JP6766510B2 - Dielectric composition and electronic components - Google Patents

Description

The present invention particularly relates to a dielectric composition suitable for use in a high temperature environment such as for automobiles and an electronic component using the dielectric composition as a dielectric layer.

Multilayer ceramic capacitors are installed in many electronic devices due to their high reliability and low cost. Specific examples of electronic devices include information terminals such as mobile phones, home appliances, and automobile electrical components. Of these, multilayer ceramic capacitors used for in-vehicle use are required to be guaranteed up to higher temperatures than multilayer ceramic capacitors used in home appliances and information terminals, and are highly insulated to maintain their functions. Sex is needed.

Furthermore, multilayer ceramic capacitors for removing surge voltage mounted in inverter circuits using power semiconductors such as SiC or GaN, which are considered to be used in the high temperature range of 150 ° C or higher, have a wide range from room temperature to at least 200 ° C. High insulation is required at temperature.

Patent Document 1 describes the chemical formula (1-), which is a dielectric ceramic composition that exhibits a sufficient dielectric constant and can obtain stable capacitance temperature characteristics and high resistivity ρ even at a high temperature of about 175 ° C. _{a) (K 1-x Na} x) (Sr 1-y-z Ba y Ca z) 2 Nb 5 O 15 -a (Ba 1-b Ca b) a tungsten bronze structure compound represented by TiO ₃ with perovskite A technique relating to a multilayer ceramic capacitor using a dielectric ceramic composition containing a mixed crystal system with a structural compound as a main component and containing 0.1 to 40 mol of sub-components with respect to 100 mol of the main component. It is disclosed.

Further, Patent Document 2 describes a dielectric containing a tungsten bronze-type composite oxide represented by the chemical formula (K _1-x Na _x ) Sr ₂ Nb ₅ O ₁₅ (however, 0 ≦ x <0.2) as a main component. In the body ceramic composition, a dielectric ceramic composition having a high resistivity at room temperature by containing 0.05 to 20 mol parts of rare earth elements and 0.05 to 40 mol parts of Mn, V, Li and the like as subcomponents. The technology of things is disclosed.

Patent Document 3, the chemical formula _{[(Ba 1-x-y} Ca x Sr y) O] m · (Ti 1-z Zr z) O 2 as a main component, the _P 2 _{O 5} as a sub-component 0.005 Disclosed is a technology that acts as a barrier layer to prevent migration of Ni ions during a high temperature load test by containing ~ 0.5% by weight (about 0.5 mol% when converted to mol%) and improves the high temperature load life. Has been done.

WO2008 / 155945 WO2008 / 102608 Japanese Unexamined Patent Publication No. 2000-124058

However, although Patent Document 1 has good insulating properties in a high temperature region (175 ° C.), the rate of change in resistivity is not mentioned. Patent Document 2 also has good insulation at room temperature because it contains various subcomponents, but does not mention specific resistance in a high temperature range, for example, 200 ° C. Further, Patent Document 3 has a high high-temperature load life by containing P ₂ O ₅ in a perovskite-type barium titanate-based material, but the resistivity at room temperature or 200 ° C. and its change thereof. The rate has not been considered.

The present invention has been made in view of the above problems, and has a high resistivity under a high temperature atmosphere of 200 ° C., which is suitable for in-vehicle use and for power devices using SiC or GaN-based semiconductors, and has a resistivity of 200 to 200 from room temperature. It is an object of the present invention to provide a dielectric composition having a small rate of change in resistivity at ° C. and an electronic component using the same.

In order to achieve the above object, the dielectric composition of the present invention is a tungsten bronze type composite represented by the chemical formula (K _1-x Na _x ) Sr ₂ Nb ₅ O ₁₅ (where 0 ≦ x ≦ 0.40). in the dielectric composition composed mainly of oxides, as the first subcomponent _{MgO, BaO, B 2 O 3} , comprises SiO _2, P 2 _{O 5,} wherein the total content of the auxiliary component composed mainly 100mol On the other hand, it is characterized in that it is 2.5 mol to 20.0 mol.

Having the above characteristics of the dielectric composition makes it possible to provide a dielectric composition having good insulating properties suitable for use in a wide range from room temperature to 200 ° C. The good insulating property means that the specific resistance is high at 200 ° C. and the rate of change of the specific resistance is small in a wide range from room temperature to 200 ° C.

Further, by using the dielectric layer made of the dielectric composition, it can be used in an in-vehicle application where it is required to be used in a low temperature region of −55 ° C. to a region of about 150 ° C., or even a higher temperature region of about 200 ° C. It is possible to provide a snubber capacitor for a power device using a required SiC or GaN-based semiconductor, a capacitor used for removing noise in an automobile engine room, and the like.

The present invention has a dielectric composition having a high specific resistance and a small change rate of the specific resistance from room temperature to 200 ° C. in a high temperature atmosphere of 200 ° C., which is suitable for in-vehicle use and power devices using SiC or GaN-based semiconductors. It is possible to provide an object and an electronic component using the object.

FIG. 1 shows a cross-sectional view of a multilayer ceramic capacitor according to an embodiment of the present invention.

First, a multilayer ceramic capacitor, which is a main application of the dielectric composition of the present invention, will be described. FIG. 1 shows a cross-sectional view of a general multilayer ceramic capacitor.

The multilayer ceramic capacitor 1 has a capacitor element main body 10 having a structure in which a dielectric layer 2 and an internal electrode layer 3 are alternately laminated. At both ends of the capacitor element body 10, a pair of external electrodes 4 that are electrically connected to the internal electrode layers 3 alternately arranged inside the capacitor element body 10 are formed. The shape of the capacitor element main body 10 is not particularly limited, but is usually a rectangular parallelepiped shape. Further, the size is not particularly limited, and may be an appropriate size according to the application.

The internal electrode layers 3 are laminated so that their end faces are alternately exposed on the surfaces of the two opposing ends of the capacitor element main body 10. The pair of external electrodes 4 are formed at both ends of the capacitor element main body 10 and are connected to the exposed end faces of the alternately arranged internal electrode layers 3 to form a capacitor circuit.

The thickness of the dielectric layer 2 is not particularly limited, but is preferably 100 μm or less, and more preferably 30 μm or less per layer. The lower limit of the thickness is not particularly limited, but is, for example, about 0.5 μm. According to the dielectric composition of the present invention, the monolithic ceramic capacitor 1 having good insulating properties can be formed even when the interlayer thickness is 0.5 μm to 30 μm.

The number of layers of the dielectric layer 2 is not particularly limited, but is preferably 20 or more, and more preferably 50 or more.

The conductive material contained in the internal electrode layer 3 is not particularly limited, but Ni, Ni alloys, Cu or Cu-based alloys are preferable. The Ni, Ni-based alloy, Cu, or Cu-based alloy may contain various trace components such as P in an amount of about 0.1% by mass or less. Further, the internal electrode layer 3 may be formed by using a commercially available electrode paste. The thickness of the internal electrode layer 3 may be appropriately determined according to the application and the like.

More preferably, the conductive material contained in the internal electrode layer 3 is a Ni or Ni-based alloy because the constituent material of the dielectric layer 2 has reduction resistance. It is more preferable that the Ni or Ni-based alloy is the main component, and that it contains one or more sub-components selected from Al, Si, Li, Cr, and Fe.

By incorporating one or more sub-components selected from Al, Si, Li, Cr, and Fe into the Ni or Ni-based alloy that is the main component of the internal electrode layer 3, Ni reacts with oxygen in the atmosphere. Before becoming NiO, oxygen reacts with the above-mentioned sub-component to form an oxide film of the sub-component on the surface of Ni. As a result, oxygen in the outside air cannot react with Ni unless it passes through the oxide film of the sub-component, so that Ni is less likely to be oxidized. As a result, even when continuously used at a high temperature of 200 ° C., deterioration of continuity and conductivity due to oxidation of the internal electrode layer containing Ni as a main component is less likely to occur.

The conductive material contained in the external electrode 4 is not particularly limited, but in the present invention, inexpensive Ni, Cu, highly heat-resistant Au, Ag, Pd, and alloys thereof can be used. The thickness of the external electrode 4 may be appropriately determined depending on the application and the like, but is usually preferably about 10 to 50 μm.

Next, the dielectric composition according to this embodiment will be described in detail.

The dielectric composition according to the present embodiment contains a tungsten bronze type composite oxide represented by the chemical formula (K _1-x Na _x ) Sr ₂ Nb ₅ O ₁₅ (where 0 ≦ x ≦ 0.40) as a main component. In the dielectric composition to be described, MgO, BaO, B ₂ O ₃ , SiO ₂ , P ₂ O ₅ are contained as the first sub-components, and the total content of the sub-components is 100 mol as the main component. It is characterized by being 5 mol to 20.0 mol.

Having the above characteristics of the dielectric composition makes it possible to provide a dielectric composition having good insulating properties suitable for use in a wide range from room temperature to 200 ° C. The factors that obtained such an effect are shown below.

The inventors have described a dielectric composition containing a tungsten bronze-type composite oxide represented by the chemical formula (K _1-x Na _x ) Sr ₂ Nb ₅ O ₁₅ (however, 0 ≦ x ≦ 0.40) as a main component. _{to, MgO, BaO, B 2 O} 3, SiO 2, whereby P 2 _O containing a predetermined amount of the first auxiliary component composed of _5, to a high temperature range of about 200 ° C. from room main cause of decrease of specific resistance It has been found that an action of suppressing the increase and movement of electrons, which are considered to be a large number of carriers, can be obtained. As a result, we believe that it has become possible to maintain high insulation in a wide temperature range from room temperature to about 200 ° C, which was difficult to achieve until now.

K of (K _1-x Na _x ) Sr ₂ Nb ₅ O _{15 in} the chemical formula is replaced with Na. The substitution amount x is 0 ≦ x ≦ 0.40. If the substitution amount x exceeds the 0.40, _MgO is characteristic of the dielectric composition according to the present embodiment, _BaO, B 2 _{O 3,} a first auxiliary component composed of SiO _2, P 2 _{O 5} However, the effect of suppressing the increase and movement of electrons, which are a large number of carriers, which is considered to be the main cause of the decrease in specific resistance, cannot be obtained, and as a result, the specific resistance at 200 ° C. decreases, and the specific resistance at 200 ° C. The rate of change in resistivity at ° C deteriorates.

Further, MgO, BaO, B ₂ O ₃ , SiO ₂ , P ₂ O ₅ are contained as the first sub-component, and the total content of the first sub-component is from 2.5 mol with respect to 100 mol of the main component. It is 20.0 mol. As a result, an action of suppressing the increase of electrons, which are a large number of carriers, which is considered to be the main cause of the decrease in resistivity, and the movement thereof can be obtained, and as a result, good insulating properties can be obtained. When the total content is less than 2.5 mol or more than 20.0 mol, the increase of electrons which are a large number of carriers or the movement of electrons cannot be suppressed, and the specific resistance at 200 ° C. becomes low. Therefore, the rate of change in resistivity deteriorates. Further, in the combination other than the above-mentioned five kinds of oxides as subcomponents, the increase of electrons which are a large number of carriers cannot be effectively suppressed, and the specific resistance at room temperature becomes low.

In a desirable embodiment of the present invention, when the first subcomponent is represented as aMgO-bBaO-cB ₂ O _3- dSiO _2- eP ₂ O ₅ , the relationship between a, b, c, d and e is a + b + c + d + e. = 1.00, 0.50 ≦ a ≦ 0.75, 0.02 ≦ b ≦ 0.15, 0.05 ≦ c ≦ 0.25, 0.05 ≦ d ≦ 0.25, 0.02 ≦ e It is preferably ≦ 0.15. Within the above range, the effect of suppressing the increase and movement of electrons, which are a large number of carriers, can be enhanced. Therefore, it is possible to increase the specific resistance at 200 ° C. and further reduce the rate of change of the specific resistance from room temperature to 200 ° C.

Further, as a desirable aspect of the present invention, the second subcomponent is further selected from La ₂ O ₃ , SnO ₂ , Y ₂ O ₃ , Sb ₂ O ₃ , Ta ₂ O ₅ , and Nb ₂ O _5. It is preferable to contain at least one or more of 0.5 mol to 5.0 mol with respect to 100 mol of the main component. As a result, it is possible to improve the withstand voltage of DC at 200 ° C. as well as good insulation.

Further, the dielectric composition contains a secondary phase containing MgO and P ₂ O _5, the case where the total area of the cross section of the dielectric composition was 100%, the area occupied the secondary phase, It is preferably 2.0% to 15.0%. Wherein A MgO and secondary phase containing _P 2 _{O 5,} and has a 3MgO _· P 2 _{O 5} system, or _{(MgO · BaO) -P 2 O} 5 based phosphate crystal structure. Also, the secondary phase in the dielectric composition, the presence content and particle morphology than 90 mol% of MgO and P ₂ O _5, the grain boundary, in the form of such segregation phase existing in the grain boundary triple point It is preferable to do so. As a result, by including the secondary phase in a predetermined amount, it is possible to keep the rate of change of the resistivity small even in a wider temperature range from room temperature to 250 ° C.

In the case of the multilayer ceramic capacitor sample which is an example of the present embodiment, the above area ratio is microsampled using FIB (Focused Ion Beam) to prepare a TEM sample of a dielectric layer, and scanning transmission is performed. It is obtained by performing STEM-EDS (Scanning Transmission Electron Microscopy-Energy Dispersive X-ray Spectrometri) mapping using an electron microscope. The field of view for mapping is 7 μm × 7 μm, and it is preferable to map 10 or more fields of view for each sample. It is also possible to obtain the area ratio by performing element mapping on the cross section of the polished dielectric layer by EPMA (Electron Probe Micro Analyzer). The field of view of the mapping at that time is 10 μm × 10 μm, and each sample may be mapped with 5 or more fields of view, and the area ratio may be calculated from the obtained element map.

As described above, since the dielectric composition according to the present embodiment exhibits good characteristics in a high temperature region, it is suitable in the operating temperature range (-55 ° C. to 200 ° C. or 250 ° C.) of a SiC or GaN-based power device. Can be used. Further, it can be suitably used as an electronic component for noise removal in a harsh environment such as an engine room of an automobile.

In the (K _1-x N _x ) Sr ₂ Nb ₅ O ₁₅ in the chemical formula, the mol ratio of each K site, Sr site, Nb site, and O site is basically 1: 2: 5: 15. However, it may be increased or decreased slightly as long as the tungsten bronze structure can be maintained.

Further, the dielectric composition according to the present embodiment may contain minute impurities and a third subcomponent as long as it does not significantly deteriorate the good insulating property which is the effect of the present invention. For example, Mn, V, Cr and the like. Therefore, the content of the main component is not particularly limited, but is, for example, 70 mol% or more and less than 98 mol% with respect to the entire dielectric composition containing the main component.

Next, a method for producing the dielectric composition according to the present embodiment will be described. As a method for producing the dielectric composition, a known method may be adopted. For example, a solid phase method in which a starting material such as an oxide powder or a carbonic acid oxide is mixed and the obtained mixed powder is heat-treated and synthesized may be adopted.

The main component (K _1-x Na _x ) Sr ₂ Nb ₅ O ₁₅ is a starting material of K ₂ CO ₃ , Na ₂ CO ₃ , SrCO ₃ , Nb ₂ O ₅ powder with an average particle size of 1.0 μm or less. Prepare. After weighing to a predetermined ratio, wet mixing is performed for a predetermined time using a ball mill or the like. After the mixed powder is dried, it is heat-treated at 1000 ° C. or lower in the air to obtain a calcined powder of (K _1-x Na _x ) Sr ₂ Nb ₅ O ₁₅ .

As the first auxiliary component, MgO, SiO ₂ , BaCO ₃ , B ₂ O ₃ , and P ₂ O ₅ powders having an average particle diameter of 1.0 μm or less are prepared as starting materials. In addition, if necessary, La ₂ O ₃ , SnO ₂ , Y ₂ O ₃ , Sb ₂ O ₃ , Ta ₂ O ₅ , and Nb ₂ O ₅ powders, which are starting materials for the second subcomponent, are prepared. After weighing these in a predetermined ratio, wet mixing is performed for a predetermined time using a ball mill or the like. Then, after the mixed powder is dried, it is heat-treated at 700 ° C. to 800 ° C. for 1 to 5 hours in the air to prepare a calcined powder as a sub-component. The dried mixed powder may be used without heat treatment.

Then, the obtained (K _1-x Na _x ) Sr ₂ Nb ₅ O ₁₅ calcined powder and the sub-component tempered powder or the sub-component mixed powder were mixed and crushed to obtain an average particle size. A mixed powder having a diameter of 0.5 μm to 2.0 μm is prepared.

Next, an example of a method for manufacturing the multilayer ceramic capacitor shown in FIG. 1 will be described.

In the multilayer ceramic capacitor 1 of the present embodiment, like the conventional multilayer ceramic capacitor, a green chip is produced by a normal printing method or a sheet method using a paste, and after firing, an external electrode is applied and fired. Manufactured by Hereinafter, the manufacturing method will be specifically described.

The mixed powder obtained above is made into a paint to prepare a paste for a dielectric layer. The paste for the dielectric layer may be an organic paint obtained by kneading a mixed dielectric powder and an organic vehicle, or may be a water-based paint.

An organic vehicle is a binder dissolved in an organic solvent. The binder used for the organic vehicle is not particularly limited, and may be appropriately selected from various ordinary binders such as ethyl cellulose and polyvinyl butyral. The organic solvent used is not particularly limited, and various organic solvents such as terpineol, butyl carbitol, and acetone may be appropriately selected depending on the method to be used such as a printing method and a sheet method.

When the paste for the dielectric layer is used as a water-based paint, a water-based vehicle in which a water-soluble binder or a dispersant is dissolved in water may be kneaded with the dielectric material. The water-soluble binder used in the water-based vehicle is not particularly limited, and for example, polyvinyl alcohol, cellulose, a water-soluble acrylic resin, or the like may be used.

The paste for the internal electrode layer is obtained by kneading the above-mentioned conductive material made of various conductive metals and alloys, or the above-mentioned various oxides, organometallic compounds, resinates and the like which become the above-mentioned conductive material after firing, and the above-mentioned organic vehicle. Prepare.

The paste for the external electrode may be prepared in the same manner as the paste for the internal electrode layer described above.

The content of the organic vehicle in each of the above-mentioned pastes is not particularly limited, and may be a normal content, for example, about 1% by mass to 5% by mass for the binder and about 10% by mass to 50% by mass for the solvent. Further, each paste may contain an additive selected from various dispersants, plasticizers, dielectrics, insulators and the like, if necessary. The total content of these is preferably 10% by mass or less.

When the printing method is used, the paste for the dielectric layer and the paste for the internal electrode layer are printed and laminated on a substrate such as PET, cut into a predetermined shape, and then peeled from the substrate to obtain a green chip.

When the sheet method is used, a green sheet is formed by using the paste for the dielectric layer, the paste for the internal electrode layer is printed on the green sheet, and then these are laminated to form a green chip.

Before firing, the green chips are debindered. As the binder removal conditions, the heating rate is preferably 5 ° C./hour to 300 ° C./hour, the holding temperature is preferably 180 ° C. to 500 ° C., and the temperature holding time is preferably 0.5 hour to 24 hours. The firing atmosphere is air or a reducing atmosphere. Further, in the above binder removal processing, to wet the N ₂ gas and mixed gas, etc., for example, it may be used to wetter like. In this case, the water temperature is preferably about 5 ° C to 75 ° C.

The holding temperature during firing is preferably 1000 ° C. to 1400 ° C., more preferably 1100 ° C. to 1350 ° C. If the holding temperature is less than the above range, densification becomes insufficient, and if it exceeds the above range, the electrode is interrupted due to abnormal sintering of the internal electrode layer, and the capacitance changes with respect to the temperature due to diffusion of the internal electrode layer constituent material. The rate tends to be large. On the other hand, if it exceeds the above range, the crystal particles may become coarse and the insulating property may be deteriorated.

The rate of temperature rise is preferably 200 ° C./hour to 5000 ° C./hour, and more preferably 1000 ° C./hour to 5000 ° C./hour. Further, in order to control the particle size distribution after sintering within the range of 0.5 μm to 5.0 μm and to suppress the volume diffusion between the crystal particles, the temperature holding time is preferably 0.5 hours to 2.0 hours. The time is more preferably 0.5 hours to 1.0 hours, and the cooling rate is preferably 100 ° C./hour to 500 ° C./hour, more preferably 200 ° C./hour to 300 ° C./hour.

Further, as an atmosphere for firing, it is preferable to use a mixed gas of humidified N ₂ and H ₂ and fire at an oxygen partial pressure of ^10-2 to ^10-9 Pa. More preferably, the oxygen partial pressure is ^10-2 to ^10-5 Pa. By firing in an atmosphere with a high oxygen partial pressure, the effect of facilitating the precipitation of the secondary phase can be obtained. However, when firing is performed in a state where the oxygen partial pressure is high, in the case of the internal electrode layer made of Ni, Ni is oxidized and the conductivity as an electrode is lowered. In this case, Ni is contained in the conductive material containing Ni as a main component, which is a more preferable embodiment of the present embodiment, with one or more subcomponents selected from Al, Si, Li, Cr, and Fe. The oxidation resistance of silicon is improved, and it is possible to secure conductivity as an internal electrode layer even in an atmosphere having a high oxygen partial pressure.

After firing, the obtained capacitor element main body is annealed as necessary. The annealing treatment conditions may be known conditions. For example, the oxygen partial pressure during the annealing treatment is preferably higher than the oxygen partial pressure during firing, and the holding temperature is preferably 1000 ° C. or lower.

Further, although the manufacturing method in which the binder removal treatment, the firing and the annealing treatment are independently performed is described above, the binder removal treatment, the firing and the annealing treatment may be continuously performed.

The capacitor element body obtained as described above is subjected to end face polishing by, for example, barrel polishing or sandblasting, and an external electrode paste is applied and fired to form an external electrode 4. Then, if necessary, a coating layer is formed on the surface of the external electrode 4 by plating or the like.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the gist of the present invention.

Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention, but the present invention is not limited to these examples. Hereinafter, the samples marked with * in the table mean that they are outside the scope of this embodiment.

Example 1
First, the main component (K _1-x Na _x ) Sr ₂ Nb ₅ O ₁₅ is K ₂ CO ₃ , Na ₂ CO ₃ , SrCO ₃ , Nb ₂ O ₅ having an average particle size of 1.0 μm or less as a starting material. The powder was prepared and weighed so as to satisfy the mol ratio shown in each sample number in Table 1. Then, ethanol as a dispersion medium was used for wet mixing with a ball mill for 17 hours. Then, the obtained mixture was dried to obtain a mixed raw material powder. Then, heat treatment was carried out in the air under the conditions of a holding temperature of 950 ° C. and a holding time of 24 hours to obtain a calcined powder as a main component.

Next, the first subcomponent and the second subcomponent are MgO, SiO ₂ , BaCO ₃ , B ₂ O ₃ , P ₂ O ₅ , La ₂ O ₃ having an average particle diameter of 1.0 μm or less as starting materials. , SnO ₂ , Y ₂ O ₃ , Sb ₂ O ₃ , Ta ₂ O ₅ , and Nb ₂ O ₅ powders were prepared and weighed so as to have the ratio shown in each sample number in Table 1. Then, ethanol was used as a dispersion medium and wet-mixed by a ball mill for 17 hours. Then, the mixed powder was dried at 80 ° C. for 24 hours, and then heat-treated in the air at 750 ° C. to 900 ° C. for 3 hours to prepare a calcined powder as an auxiliary component. Then, with respect to 100 mol of the prepared (K _1-x Na _x ) Sr ₂ Nb ₅ O ₁₅ calcined powder, the calcined powder of the subcomponent was weighed so as to have the blending ratio shown in each sample number in Table 1. , (K _1-x Na _x ) Sr ₂ Nb ₅ O ₁₅ calcined powder and subcomponent calcined powder were mixed and pulverized in a ball mill for 24 hours, and the average particle size was 0.5 μm to 2.0 μm. A mixed calcined powder was prepared.

To 1000 g of the mixed calcined powder obtained above, 700 g of a solvent obtained by mixing a toluene + ethanol solution, a plasticizer and a dispersant at a ratio of 90: 6: 4 is added to a basket, which is a usual well-known dispersion method. The mixture was dispersed for 2 hours using a mill to prepare a paste for a dielectric layer. The viscosity of each of these pastes was adjusted to about 200 cps.

Ni having an average particle size of 0.2 μm and oxides of Al and Si having an average particle size of 0.1 μm or less were prepared as raw materials for the internal electrode layer, and the total amount of Al and Si as subcomponents was 5% by mass with respect to Ni. Weighed so that Then, the raw material powder having an average particle size of 0.20 μm was prepared by heat-treating in a mixed gas of N ₂ and H ₂ humidified at 1200 ° C. or higher and crushing the mixture using a ball mill or the like.

100% by mass of the raw material powder, 30% by mass of an organic vehicle (8% by mass of ethyl cellulose resin dissolved in 92% by mass of butyl carbitol), and 8% by mass of butyl carbitol are kneaded and pasted by three rolls. , A paste for the internal electrode layer was obtained.

Then, using the prepared paste for the dielectric layer, a green sheet was formed on the PET film so that the thickness after drying was 12 μm. Next, the internal electrode layer was printed in a predetermined pattern using the paste for the internal electrode layer, and then the sheet was peeled off from the PET film to prepare a green sheet having the internal electrode layer. Next, a plurality of green sheets having an internal electrode layer were laminated and pressure-bonded to form a green laminate, and the green laminate was cut to a predetermined size to obtain a green chip.

Next, the obtained green chips were subjected to a binder removal treatment, a firing treatment, and an annealing treatment to obtain a laminated ceramic sintered body. The conditions for the binder removal treatment, firing and annealing treatment are as follows. In addition, a wetter was used to humidify each atmospheric gas.

(Binder removal processing)
Temperature rise rate: 100 ° C / hour Holding temperature: 400 ° C
Temperature holding time: 8.0 hours Atmospheric gas: Mixed gas of humidified N ₂ and H ₂ (firing)
Temperature rise rate: 1000 ° C / hour Holding temperature: 1100 ° C to 1300 ° C
Temperature holding time: 1.0 hour Cooling rate: 200 ° C./hour Atmospheric gas: Mixed gas of humidified N ₂ and H ₂ Oxygen partial pressure: ^10-6 to ^10-9 Pa
(Annealing process)
Holding temperature: 1000 ° C
Temperature holding time: 2.0 hours temperature rise, temperature decrease rate: 200 ° C / hour Atmospheric gas: Humidified N ₂ gas

As a result of analyzing the composition of each sample using the ICP emission spectroscopic analysis method for each of the obtained laminated ceramic sintered bodies, it was confirmed that the values were almost the same as those of the dielectric compositions shown in Table 1. did.

After polishing the end face of the obtained multilayer ceramic sintered body by sandblasting, an In—Ga eutectic alloy was applied as an external electrode, and the sample No. having the same shape as the multilayer ceramic capacitor shown in FIG. 1 was applied. Sample No. 1 to sample No. 59 multilayer ceramic capacitor samples were obtained. The sizes of the obtained multilayer ceramic capacitor samples are all 3.2 mm × 1.6 mm × 1.2 mm, the thickness of the dielectric layer is 10 μm, the thickness of the internal electrode layer is 2 μm, and the dielectric sandwiched between the internal electrode layers. The number of layers was 50.

The obtained sample No. Sample No. 1 to sample No. For 59 multilayer ceramic capacitor samples, the specific resistance at room temperature, the specific resistance at 200 ° C. and the rate of change of the specific resistance at that time, and the DC withstand voltage at 200 ° C. were measured and evaluated by the methods shown below, and are shown in Table 2. ..

[Method for measuring resistivity at room temperature and 200 ° C]
Insulation resistance was applied to a multilayer ceramic capacitor sample at room temperature (20 ° C) and 200 ° C with a digital resistance meter (R8340 manufactured by ADVANTEST) under the conditions of a measurement voltage of 50 V (electric field strength 5 V / μm) and a measurement time of 60 seconds. It was measured. The value of resistivity was calculated from the electrode area and the dielectric thickness of the multilayer ceramic capacitor sample. It is preferable that the specific resistance is high, and it is judged that 5.00 × 10 ¹⁰ Ωm or more at room temperature and 1.00 × 10 ⁹ Ωm or more at 200 ° C. are good. In Table 2, the specific resistance is logarithmically displayed. When 5.00 × 10 ¹⁰ is logarithmically displayed, it is 10.7, and when 1.00 × 10 ⁹ Ωm is logarithmically displayed, it is 9.0.

[Method of calculating the rate of change of resistivity]
The rate of change of the specific resistance was calculated by using the formula (1) shown below for the rate of change of the specific resistance Log (ρ _{(200 ° C)} ) at _{200 ° C.} with respect to the specific resistance Log (ρ _(RT) ) at room temperature.
Rate of change (%) =
[Log (ρ _{(200 ° C.)} )-Log (ρ _(RT) )] / Log (ρ _(RT) ) × 100 ... (1)
The smaller the rate of change in the specific resistance, the more preferable it was, and it was judged that it was good that the rate of change was -20% or less, more preferably -15% or less.

[DC withstand voltage measurement method]
A DC voltage was applied to the monolithic ceramic capacitor sample at a boost rate of 100 V / sec at 200 ° C., and a DC withstand voltage was defined when the leakage current exceeded 10 mA. The withstand voltage of DC is preferably 50 V / μm or more, and 100 V / μm or more is judged to be good.

According to the results shown in Table 2, the sample No. 1-Sample No. Of the 59, the monolithic ceramic capacitor sample within the range of the present embodiment has an effect of suppressing the increase and movement of electrons, which are a large number of carriers, which are considered to be the main cause of the decrease in resistivity, and therefore the ratio at room temperature. The Log (ρ _(RT) ) of the resistance is 10.7 or more, the Log (ρ _{(200 ° C)} ) of the specific resistance at _{200 ° C} is as high as 9.0 or more, and the rate of change of the specific resistance is -20% or less. It was confirmed that it had a good insulating property of being small.

On the other hand, sample No. 5. Sample No. 10. Sample No. Reference numeral ₁₅ is a large number of carriers considered to be the main cause of the decrease in resistivity because _x of the chemical formula (K _1-x Na _x ) Sr ₂ Nb ₅ O ₁₅ exceeds 0.40 and is outside the range of this embodiment. It is difficult to obtain the effect of suppressing the increase of electrons and their movement, and the Log (ρ _(RT) ) of the specific resistance at room temperature is less than 10.7, and the Log (ρ _{(200 ° C)} ) of the specific resistance at _{200 ° C} is 9. It was confirmed that it was as low as less than .0 and the rate of change of resistivity exceeded -20%.

In addition, sample No. 11-Sample No. In No. 15, since the content of the first subcomponent is outside the range of the present embodiment, it is difficult to obtain the effect of suppressing the increase and movement of electrons, which are a large number of carriers, which are considered to be the main cause of the decrease in resistivity. The Log (ρ _(RT) ) of the specific resistance at room temperature is less than 10.7, the Log (ρ _{(200 ° C)} ) of the specific resistance at _{200 ° C} is as low as less than 9.0, and the rate of change of the specific resistance is-. It was confirmed that it exceeded 20%.

Further, _MgO is the first subcomponent, _BaO, of _{B 2 O 3, SiO 2,} P 2 O 5, which is outside the scope of this embodiment that does not include even one any sample No. 16-Sample No. In No. 20, the Log (ρ _(RT) ) of the specific resistance at room temperature is less than 10.7, the Log (ρ _{(200 ° C)} ) of the specific resistance at _{200 ° C} is as low as less than 9.0, and the change in the specific resistance It was confirmed that the rate exceeded -20%.

When the first sub-component is represented by aMgO-bBaO-cB ₂ O _3- dSiO _2- eP ₂ O ₅ , the relationship of a, b, c, d, e is the range of the present embodiment a + b + c + d + e = 1.00, 0.50 ≦ a ≦ 0.75, 0.02 ≦ b ≦ 0.15, 0.05 ≦ c ≦ 0.25, 0.05 ≦ d ≦ 0.25, 0.02 ≦ e ≦ Sample No. that satisfies 0.15. 22-Sample No. 24, Sample No. 27-Sample No. 30, sample No. 33-Sample No. 35, Sample No. 38-Sample No. 40, Sample No. 43-Sample No. 46, Sample No. 48-Sample No. Since 59 was able to further enhance the effect of suppressing the increase and movement of electrons, which are a large number of carriers, the Log (ρ _(RT) ) of the specific resistance at room temperature was 11.5 or more, and the specific resistance at 200 ° C. It was confirmed that it is possible to realize a higher insulating property with a high Log (ρ _{(200 ° C.)} ) of 10.0 or more and a rate of change of specific resistance of -15% or less.

Further, 0.5 mol to 5.0 mol of at least one or more second subcomponents selected from La ₂ O ₃ , SnO ₂ , Y ₂ O ₃ , Sb ₂ O ₃ , Ta ₂ O ₅ , and Nb ₂ O ₅ Contains sample No. 49-Sample No. In No. 59, the Log (ρ _(RT) ) of the specific resistance at room temperature is 11.5 or more, the Log (ρ _{(200 ° C)} ) of the specific resistance at _{200 ° C} is as high as 10.0 or more, and the change in the specific resistance In addition to good insulation with a resistivity of -15% or less, it was confirmed that the DC withstand voltage at 200 ° C. was 100 V / μm or more. As described above, by containing a predetermined amount of the second sub-component, it was possible to improve not only good insulating properties but also new physical properties such as high DC withstand voltage.

Example 2
Then, by way of specific examples of the case containing the secondary phase containing MgO and P ₂ O ₅ in the dielectric composition, it is described.

First, the sample No. prepared in Example 1. 49-Sample No. We prepared 59 green chips. The prepared green chips were subjected to the following debinder treatment, firing and annealing treatment to prepare a laminated ceramic sintered body containing a secondary phase.
The oxygen partial pressure and the annealing treatment conditions of the firing conditions are different from the conditions of Example 1.

(Binder removal processing)
Temperature rise rate: 100 ° C / hour Holding temperature: 400 ° C
Temperature holding time: 8.0 hours Atmospheric gas: Mixed gas of humidified N ₂ and H ₂ (firing)
Temperature rise rate: 1000 ° C / hour Holding temperature: 1100 ° C to 1300 ° C
Temperature holding time: 1.0 hour Cooling rate: 200 ° C./hour Atmospheric gas: Mixed gas of humidified N ₂ and H ₂ Oxygen partial pressure: 10 ^-3 to ^10-5 Pa
(Annealing process)
Holding temperature: 800 ° C to 850 ° C
Temperature holding time: 5.0 hours Temperature rise, temperature decrease rate: 200 ° C / hour Atmospheric gas: Humidified N ₂ gas

As a result of analyzing the composition of each sample using the ICP emission spectroscopic analysis method for each of the obtained laminated ceramic sintered bodies, it was confirmed that the values were almost the same as those of the dielectric compositions shown in Table 3. did.

なお、実施例１で作製した積層セラミックコンデンサ試料と区別するため、実施例２で作製したものは、新たに試料番号を付与している。（試料Ｎｏ．６０〜試料Ｎｏ．７０）

In order to distinguish from the multilayer ceramic capacitor sample prepared in Example 1, the sample prepared in Example 2 is newly assigned a sample number. (Sample No. 60 to Sample No. 70)

The obtained laminated ceramic fired body was polished in the same manner as in Example 1, attached with an external electrode, and sample No. of the same shape. From 60, sample No. 70 multilayer ceramic capacitor samples were obtained.

The obtained sample No. From 60, sample No. For 70 multilayer ceramic capacitor samples, the specific resistance at room temperature, 200 ° C, 250 ° C and the rate of change of the specific resistance at that time, the DC withstand voltage at 200 ° C, and the area ratio of the secondary phase by image analysis are measured by the methods shown below. It was measured and evaluated and shown in Table 4.

[Method for measuring resistivity at room temperature, 200 ° C and 250 ° C]
With respect to the multilayer ceramic capacitor sample, at room temperature (20 ° C), 200 ° C, 250 ° C, with a digital resistance meter (R8340 manufactured by ADVANTEST), the measurement voltage is 10 V (electric field strength 5 V / μm), and the measurement time is 60 seconds. The insulation resistance was measured. The value of resistivity was calculated from the electrode area and the dielectric thickness of the multilayer ceramic capacitor sample. It is preferable that the specific resistance is high, and it is judged that 5.00 × 10 ¹⁰ Ωm or more at room temperature and 1.00 × 10 ⁹ Ωm or more at 200 ° C. and 250 ° C. are good. In Table 4, the specific resistance is logarithmically displayed. When 5.00 × 10 ¹⁰ is logarithmically displayed, it is 10.7, and when 1.00 × 10 ⁹ Ωm is logarithmically displayed, it is 9.0.

[Method of calculating the rate of change of resistivity]
The rate of change of the specific resistance is the rate of change of the specific resistance Log (ρ _{(200 ° C or 250 ° C)} ) at _{200 ° C. or 250 ° C.} with respect to the specific resistance Log (ρ _(RT) ) at room temperature. ) Was used.
Rate of change (%) =
[Log (ρ _{(200 ° C. or 250 ° C.)} )-Log (ρ _(RT) )] / Log (ρ _(RT) ) × 100 ... (2)
The smaller the rate of change in the specific resistance, the more preferable it was, and it was judged that it was good that the rate of change was -20% or less, more preferably -15% or less.

[DC withstand voltage measurement method]
A DC voltage was applied to the monolithic ceramic capacitor sample at a boost rate of 100 V / sec at 200 ° C., and a DC withstand voltage was defined when the leakage current exceeded 10 mA. The withstand voltage of DC is preferably 50 V / μm or more, and 100 V / μm or more is judged to be good.

[Area ratio of secondary phase by image analysis]
The multilayer ceramic capacitor sample obtained by firing was microsampled using a FIB (Focused Ion Beam) to prepare a TEM sample of a dielectric layer. STEM-EDS (Scanning Transmission Electron Microscopy-Energy Dispersive X-ray Spectrometery) mapping was performed on this TEM sample using JEM2200FS, which is a scanning transmission electron microscope manufactured by JEOL. The field of view for mapping was 7 μm × 7 μm, and 10 or more fields of view were mapped for each sample. Using elemental map obtained by these methods, and Mg, P is a major element of 3MgO _· P 2 _{O 5} based phosphate _{crystals, (MgO · BaO) -P 2} O 5 based phosphate crystals The areas of Mg, Ba, and P, which are the main component elements of the above, were specified, and the area ratio of each was calculated using the average area of the results of each of 10 or more visual fields, and the area occupied by the entire secondary phase was calculated. In the present embodiment, in order to reduce the rate of change of resistivity in a wider temperature range from room temperature to 250 ° C., it is judged that the area occupied by the secondary phase is 2.0% to 15.0%. did.

なお、前記表４中の〇は、二次相が存在していることを意味している。

In addition, 〇 in Table 4 above means that a secondary phase exists.

According to Table 4, in the sample in which the secondary phase is present and the area ratio thereof is 2.0% to 15%, the rate of change of the resistivity at 250 ° C. with respect to the resistivity at room temperature is -20% or less. It was confirmed that it is possible to maintain good insulation even in a wider temperature range.

It should be considered that the embodiments and examples disclosed this time are exemplary in all respects and not restrictive. The scope of the present invention is not shown in the above embodiments and examples, but is indicated by the claims and is intended to include all modifications and modifications within the meaning and scope equivalent to the claims.

Since it has good insulation in a wide temperature range from room temperature to 200 ° C or 250 ° C, it is mounted in an environment close to an engine room for in-vehicle use, and in the vicinity of a power device using SiC or GaN-based semiconductors. It can also be applied to applications as electronic components.

1 Multilayer ceramic capacitor 2 Dielectric layer 3 Internal electrode layer 4 External electrode 10 Capacitor element body

Claims (5)

In the dielectric composition containing a tungsten bronze-type composite oxide as a main component represented by the chemical formula (K _1-x Na _x ) Sr ₂ Nb ₅ O ₁₅ (however, 0 ≦ x ≦ 0.40), the first It contains MgO, BaO, B ₂ O ₃ , SiO ₂ and P ₂ O ₅ as sub-components, and the total content of the first sub-component is 2.5 mol to 20.0 mol with respect to 100 mol of the main component. A dielectric composition comprising. When the first sub-component is represented by aMgO-bBaO-cB ₂ O _3- dSiO _2- eP ₂ O ₅ , the relationship between a, b, c, d and e is a + b + c + d + e = 1.00.
0.50 ≤ a ≤ 0.75
0.02 ≤ b ≤ 0.15
0.05 ≤ c ≤ 0.25
0.05 ≤ d ≤ 0.25
0.02 ≤ e ≤ 0.15
The dielectric composition according to claim 1, wherein the dielectric composition is characterized by the above. Further, as the second subcomponent, at least one selected from La ₂ O ₃ , SnO ₂ , Y ₂ O ₃ , Sb ₂ O ₃ , Ta ₂ O ₅ and Nb ₂ O ₅ is added to 100 mol of the main component. The dielectric composition according to claim 1 or 2, wherein the dielectric composition contains 0.5 mol to 5.0 mol. The dielectric composition contains a secondary phase containing MgO and P ₂ O _5, the case where the total area of the cross section of the dielectric composition was 100%, the area of the occupied secondary phases in the cross-section The dielectric composition according to any one of claims 1 to 3, wherein the dielectric composition is 2.0% to 15.0%. An electronic component having a dielectric layer and an internal electrode layer, wherein the dielectric layer comprises the dielectric composition according to any one of claims 1 to 4.

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