WO2024004393A1 - 積層セラミックコンデンサ - Google Patents

積層セラミックコンデンサ Download PDF

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WO2024004393A1
WO2024004393A1 PCT/JP2023/017695 JP2023017695W WO2024004393A1 WO 2024004393 A1 WO2024004393 A1 WO 2024004393A1 JP 2023017695 W JP2023017695 W JP 2023017695W WO 2024004393 A1 WO2024004393 A1 WO 2024004393A1
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ceramic
internal electrodes
internal electrode
ceramic capacitor
multilayer ceramic
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French (fr)
Japanese (ja)
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隆志 大原
英靖 大西
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to KR1020247039531A priority Critical patent/KR20250002677A/ko
Priority to CN202380028710.2A priority patent/CN118901113A/zh
Priority to JP2024530347A priority patent/JP7711847B2/ja
Publication of WO2024004393A1 publication Critical patent/WO2024004393A1/ja
Priority to US18/608,997 priority patent/US20240222015A1/en
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    • 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
    • H01G4/005—Electrodes
    • H01G4/008—Selection of materials
    • H01G4/0085—Fried electrodes
    • 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
    • C04B35/468—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 based on barium 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
    • 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
    • C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
    • 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
    • H01G4/005—Electrodes
    • H01G4/012—Form of non-self-supporting electrodes
    • 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
    • H01G4/1218—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
    • 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
    • H01G4/1236—Ceramic dielectrics characterised by the ceramic dielectric material based on zirconium oxides or zirconates
    • 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
    • H01G4/228—Terminals
    • H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
    • H01G4/2325—Terminals electrically connecting two or more layers of a stacked or rolled capacitor characterised by the material of the terminals
    • 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
    • H01G4/30—Stacked capacitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to a multilayer ceramic capacitor, and particularly to the composition of internal electrodes provided in the multilayer ceramic capacitor.
  • a multilayer ceramic capacitor usually includes a multilayer body and a multilayer structure including a plurality of laminated dielectric layers made of ceramic and a plurality of internal electrodes each disposed along a plurality of interfaces between the dielectric layers.
  • a plurality of external electrodes are provided on the outer surface and electrically connected to the internal electrodes.
  • the internal electrode includes a plurality of first internal electrodes and a plurality of second internal electrodes arranged alternately in the stacking direction of the laminate, and the external electrode includes a first external electrode electrically connected to the first internal electrode. and a second external electrode electrically connected to the second internal electrode.
  • the temperature at which the conductive metal particles contained in the conductive paste film that will become the internal electrodes is sintered is higher than the temperature at which the ceramic constituting the dielectric layer is sintered. Since the metal particles contained in the internal electrodes are low, the metal particles contained in the internal electrodes are sintered first. This causes a reduction in the coverage of the internal electrodes. Particularly, in the case of internal electrodes that are thin, such as having a thickness of 1 ⁇ m or less, the coverage tends to decrease, and such a decrease in coverage tends to hinder an increase in capacity.
  • the temperature at which the conductive metal particles contained in the conductive paste film that will become the internal electrodes is sintered must be needs to be higher.
  • the temperature at which the metal particles contained in the conductive paste film, which is to become the internal electrode, sinter can be brought closer to the temperature at which the ceramic forming the dielectric layer starts sintering, and the internal electrode and dielectric layer The shrinkage timing during sintering can be brought closer to each other. As a result, the coverage of the internal electrodes becomes high, and a large capacity can be realized.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2016-318057
  • a ceramic material having a composition similar to that of the ceramic constituting the dielectric layer that is, a co-material.
  • the co-material By adding the co-material, it is possible to shift the sintering timing of the metal particles contained in the conductive paste film that will become the internal electrode to a higher temperature side, and the metal particles contained in the conductive paste film are sintered.
  • the temperature can be brought close to the temperature at which the ceramic forming the dielectric layer is sintered.
  • an object of the present invention is to provide a multilayer ceramic capacitor including internal electrodes that can maintain relatively high coverage even when the layers are thinned.
  • a multilayer ceramic capacitor according to the present invention includes a multilayer body including a plurality of stacked dielectric layers made of ceramic and a plurality of internal electrodes respectively arranged along a plurality of interfaces between the dielectric layers.
  • the internal electrode contains a silver/palladium alloy as a conductive component, and at least one selected from (Ag 0.7 , Pd 0.3 )TiO 3 , NaTiO 3 and EuTiO 3 . It is characterized by including.
  • At least one selected from (Ag 0.7 , Pd 0.3 )TiO 3 , NaTiO 3 and EuTiO 3 contained in the internal electrode increases the coverage of the internal electrode containing a silver/palladium alloy as a conductive component. Contribute to Therefore, even if the internal electrodes are made thinner, the coverage of the internal electrodes does not decrease, and it is possible to prevent an increase in the capacity of the multilayer ceramic capacitor from being hindered.
  • FIG. 1 is a cross-sectional view schematically showing a multilayer ceramic capacitor 1 according to an embodiment of the present invention.
  • the multilayer ceramic capacitor 1 includes a multilayer body 2.
  • the laminate 2 includes a plurality of laminated dielectric layers 3 made of ceramic, and a plurality of internal electrodes 4 and 5 arranged along the interface between the plurality of dielectric layers 3.
  • the internal electrodes 4 and 5 are classified into a plurality of first internal electrodes 4 and a plurality of second internal electrodes 5, which are alternately arranged in the stacking direction of the laminate 3.
  • a first external electrode 6 and a second external electrode 7 are provided on the outer surface of the laminate 2, more specifically, on each opposing end surface.
  • the first external electrode 6 is electrically connected to the first internal electrode 4
  • the second external electrode 7 is electrically connected to the second internal electrode 5 .
  • the dielectric layer 3 is made of, for example, a ceramic whose main component is ABO 3 (A is at least one of Ba, Ca, and Sr, and B is at least one of Ti and Zr). Become. Further, the ceramic may have the above-mentioned ABO 3 as a main component, and may further contain at least one of Mn, Mg, Si, Y, Dy, and Gd as a subcomponent.
  • Internal electrodes 4 and 5 contain a silver/palladium alloy as a conductive component. Further, as a characteristic composition, the internal electrodes 4 and 5 contain at least one selected from (Ag 0.7 , Pd 0.3 )TiO 3 , NaTiO 3 and EuTiO 3 . (Ag 0.7 , Pd 0.3 )TiO 3 , NaTiO 3 and EuTiO 3 have an illuminite crystal structure.
  • the dielectric layer 3 is made of a ceramic whose main component is at least one selected from BaTiO 3 , SrTiO 3 and CaZrO 3
  • the internal electrodes 4 and 5 contains a silver/palladium alloy as a conductive component, contains at least one selected from (Ag 0.7 , Pd 0.3 )TiO 3 , NaTiO 3 and EuTiO 3 as a ceramic material, and optionally a dielectric layer 3 It further contains at least one selected from BaTiO 3 , SrTiO 3 and CaZrO 3 contained in .
  • the external electrodes 6 and 7 are formed, for example, by applying a conductive paste containing Ag or Cu as a main conductive component to the end surface of the laminate 2 and baking it. If necessary, for example, Ni plating and Sn plating may be applied on the thick film formed by baking.
  • the multilayer ceramic capacitor 1 is manufactured, for example, through the following steps. First, a ceramic slurry containing ceramic raw material powder having the composition as described above is prepared. Next, a suitable sheet forming method is applied to the ceramic slurry to form a ceramic green sheet. Next, a conductive paste to become each of the internal electrodes 4 and 5 is applied by printing or the like onto a predetermined ceramic green sheet among the plurality of ceramic green sheets. Next, a plurality of ceramic green sheets are laminated and pressed together to obtain a green laminate. The green laminate is then fired. In this firing step, the ceramic green sheet becomes the dielectric layer 3. Thereafter, external electrodes 6 and 7 are formed on the end faces of the laminate 3.
  • the conductive paste to become the internal electrodes 4 and 5 used in manufacturing the multilayer ceramic capacitor 1 described above is preferably produced as follows.
  • the first step is to prepare a ceramic powder slurry containing ceramic powder, an organic solvent, and a dispersant
  • the second step is to prepare a metal powder slurry containing a conductive metal powder, an organic solvent, and a dispersant.
  • a third step of preparing an organic vehicle containing an organic resin component and an organic solvent is to prepare a fourth step of mixing the ceramic powder slurry, metal powder slurry, and organic vehicle.
  • a ceramic powder slurry is prepared by mixing ceramic powder and a dispersant into an organic solvent.
  • the ceramic powder used includes, for example, at least one selected from (Ag 0.7 , Pd 0.3 )TiO 3 as an ABO 3 oxide, NaTiO 3 and EuTiO 3 , and in addition, A material made of at least one selected from BaTiO 3 , SrTiO 3 and CaZrO 3 may be used.
  • the conductive metal powder contained in the metal powder slurry produced in the second step described below contains a silver/palladium alloy, (Ag 0.7 , Pd 0.3 )TiO 3 , NaTiO 3 and EuTiO as the above-mentioned ABO 3 oxides are used.
  • 3 is a specific ionic radius in which the ratio of the ionic radius of the A-site element in ABO 3 in the 6-coordination to the 6-coordination ionic radius of the silver/palladium alloy is 0.96 or more and 1.10 or less. becomes an ABO 3 type oxide.
  • the metal powder slurry prepared in the second step Reactions that may occur with the conductive metal powder contained therein can be suppressed.
  • the ceramic powder has the above-mentioned ABO trioxide as a main component, and may further contain at least one of Mn, Mg, Si, Y, Dy, and Gd as a subcomponent. When such subcomponents are contained, grain growth of ceramic particles is suppressed, and sintering of metal particles may be effectively suppressed.
  • an anionic polymer dispersant for example, an anionic polymer dispersant can be used, and as the organic solvent, for example, dihydroterpineol can be used.
  • a metal powder slurry is prepared by mixing conductive metal powder and a dispersant into an organic solvent.
  • a conductive metal powder for example, a powder made of an alloy of 70 atm % silver and 30 atm % palladium is used.
  • the dispersant and organic solvent used in the second step those similar to those used in the first step can be used.
  • an organic vehicle is produced by mixing an organic resin component with an organic solvent.
  • the organic resin component for example, ethyl cellulose resin can be used.
  • the organic solvent used in the third step can also be the same as that used in the first step.
  • the conductive paste includes a ceramic powder slurry selected from (Ag 0.7 , Pd 0.3 )TiO 3 , NaTiO 3 and EuTiO 3 as ABO 3 oxides of a specific ionic radius, as described above. Since the internal electrodes 4 and 5 included in the multilayer ceramic capacitor 1 manufactured through the firing process contain at least one type of ceramic powder, the internal electrodes 4 and 5 are at least one selected from (Ag 0.7 , Pd 0.3 )TiO 3 , NaTiO 3 and EuTiO 3 . This includes one type.
  • a silver/palladium alloy powder consisting of an alloy of 70 atm% silver and 30 atm% palladium was prepared as the conductive metal powder contained in the conductive paste for forming internal electrodes.
  • BaTiO 3 and CaZrO are used as ABO 3 oxides having a specific ionic radius constituting the ceramic powder contained in the conductive paste for forming internal electrodes. 3 and SrTiO 3 were prepared. Table 1 shows the "crystal structure", “coordination number", "A-site element”, and "ion radius” for these ABO trioxides .
  • Ba, Ca, and Sr are 12-coordinated in the original perovskite structure, Ba, Ca, and Sr also have 6-coordinated elements (Ag/Pd, Na, Eu) in the illuminite structure. When it is dissolved in solid solution, it is 6-coordinated, so the "ionic radius" in Table 1 shows the value for 6-coordinated.
  • Example 1 Main component of ceramic constituting dielectric layer: BaTiO 3 1.
  • BaTiO 3 -based ceramic raw material constituting the dielectric layer As starting materials, the main component BaCO 3 and TiO 2 powders were weighed, mixed in a ball mill for 72 hours, and then heat treated at a top temperature of 1000°C for 2 hours. A heat-treated powder was obtained.
  • MnO, Dy 2 O 3 , MgO, SiO 2 and BaCO 3 powders were prepared as subcomponents, and the subcomponent powders were 100BaTiO 3 +0.5Mn+1.0Dy+1.0Mg+1.0Si+2. The powders were weighed so as to have a composition ratio of 0Ba, and these subcomponent powders were added to the heat-treated powder, mixed for 24 hours in a ball mill, and then dried to obtain a BaTiO 3 ceramic raw material powder.
  • the conductive paste for forming internal electrodes contained the "ABO trioxide " powder shown in Table 2 below and the BaTiO 3 ceramic raw material powder for the dielectric layer. It was used as a ceramic powder.
  • ABO 3 oxide powders and BaTiO 3 -based ceramic raw material powder were weighed so as to have the "addition ratio" shown in Table 2, and these powders, dihydroterpineol as an organic solvent, and anion as a dispersant were weighed.
  • a ceramic powder slurry was prepared by pre-mixing the mixture and the polymer dispersant using a medium-free stirring mill, and then performing a dispersion treatment using a medium-stirring mill (first step).
  • a metal powder slurry was prepared by dispersing silver/palladium alloy powder as a conductive metal powder, dihydroterpineol as an organic solvent, and an anionic polymer dispersant as a dispersant using a three-roll mill. (Second step).
  • the metal powder slurry and the ceramic powder slurry were added to the organic vehicle and mixed and dispersed to produce a conductive paste for forming internal electrodes (fourth step).
  • Table 2 shows the ratio of the ionic radius of the A-site element in 6-coordination to the ionic radius in 6-coordination of the silver/palladium alloy to be included in the internal electrode, i.e., "ionic radius ratio (A-site element/ Ag 0.7 Pd 0.3 alloy)” is shown.
  • ionic radius ratio A-site element/ Ag 0.7 Pd 0.3 alloy
  • Multilayer Ceramic Capacitor A ceramic slurry containing the BaTiO 3 ceramic raw material powder prepared in 1 above was prepared, and then a doctor blade method was applied to the ceramic slurry to form a ceramic green sheet. Next, the conductive paste for forming internal electrodes prepared in 2 above was applied onto a predetermined ceramic green sheet among the plurality of ceramic green sheets by screen printing. Next, a plurality of ceramic green sheets were laminated and pressed together to obtain a green laminate. The green laminate was then fired. Thereafter, external electrodes were formed on the end faces of the sintered laminate to produce a multilayer ceramic capacitor as a sample.
  • the internal electrode and dielectric layer located at the center in the height direction of the laminate provided in the multilayer ceramic capacitor serving as a sample were peeled off from each other by electric field peeling.
  • the vicinity of the exposed central part of the internal electrode was observed using a microscope at a magnification of 100 times. Then, by analyzing the obtained images, the ratio of the area occupied by the conductive film as the internal electrode in the exposed portion was determined as the "coverage” shown in Table 2. If the “coverage” is 80% or more, it is judged as good, and enter “ ⁇ ” in the “evaluation” column.If the "coverage” is lower than 80%, it is judged as poor, and in the "evaluation” column, write " ⁇ ". ⁇ ” was entered.
  • Samples 1 to 6 in Table 2 have an “evaluation” of “ ⁇ ”.
  • the internal electrode contains one of (Ag 0.7 , Pd 0.3 )TiO 3 , NaTiO 3 and EuTiO 3 as an ABO 3 oxide. Further, the internal electrode contains a silver/palladium alloy as a conductive component.
  • the ionic radius of the silver/palladium alloy in six coordinations is 1.06 ⁇ .
  • the ionic radii of the A-site elements of (Ag 0.7 , Pd 0.3 )TiO 3 , NaTiO 3 and EuTiO 3 in the 6-coordination of ABO 3 oxides contained in the internal electrodes in Samples 1 to 6 are as shown in Table 1. 1, they are 1.06 ⁇ , 1.02 ⁇ and 1.17 ⁇ , respectively.
  • the ratio of the ionic radius of the element at the A site in ABO 3 in the 6-coordination to the ionic radius in the 6-coordination of the silver/palladium alloy that is, the "ion radius ratio” is 0.96 or more and 1.10 or less.
  • the ratio of the 6-coordinate ionic radius of Ba to the 6-coordinate ionic radius of the silver/palladium alloy, ie, the "ionic radius ratio" is 1.27. Therefore, the "ion radius ratio" was outside the range of 0.96 or more and 1.10 or less, and the coverage was as low as 75%.
  • the "ion radius ratio" was out of the range of 0.96 or more and 1.10 or less, and BaTiO3 was expelled from the internal electrode part, which did not improve the heat resistance of the internal electrode and resulted in low coverage. It is assumed that it was
  • Example 2 Main component of ceramic constituting dielectric layer: CaZrO 3 1.
  • CaZrO 3 -based ceramic raw material constituting the dielectric layer As starting materials, powders of main components CaCO 3 and ZrO 2 and powders of MnO, SiO 2 and MgO as subcomponents were weighed and heated in a ball mill for 72 hours. After mixing, the mixture was heat treated at a top temperature of 1000° C. for 2 hours to obtain a CaZrO 3 ceramic raw material powder.
  • the conductive paste for forming internal electrodes contained the "ABO trioxide " powder shown in Table 3 below and the CaZrO 3 -based ceramic raw material powder for the dielectric layer. It was used as a ceramic powder.
  • Table 3 shows "ion radius ratio (A site element/Ag 0.7 Pd 0.3 alloy)" as in Table 2.
  • Table 17 shows "ion radius ratio (A site element/Ag 0.7 Pd 0.3 alloy)" as in Table 2.
  • Multilayer Ceramic Capacitor A ceramic slurry containing the CaZrO 3 ceramic raw material powder prepared in 1 above was prepared, and then a doctor blade method was applied to the ceramic slurry to form a ceramic green sheet. Thereafter, a multilayer ceramic capacitor serving as a sample was manufactured through the same steps as in Experimental Example 1.
  • Samples 11 to 16 in Table 3 have an “evaluation” of “ ⁇ ”.
  • the internal electrode contains one of (Ag 0.7 , Pd 0.3 )TiO 3 , NaTiO 3 and EuTiO 3 as an ABO 3 oxide. Further, the internal electrode contains a silver/palladium alloy as a conductive component.
  • the ionic radius of the silver/palladium alloy in six coordinations is 1.06 ⁇ .
  • the ionic radii of the A-site elements of (Ag 0.7 , Pd 0.3 )TiO 3 , NaTiO 3 and EuTiO 3 in the 6-coordination of each ABO 3 oxide contained in the internal electrodes in Samples 11 to 16 are as shown in Table 1. 1, they are 1.06 ⁇ , 1.02 ⁇ and 1.17 ⁇ , respectively.
  • the ratio of the ionic radius of the element at the A site in ABO 3 in the 6-coordination to the ionic radius in the 6-coordination of the silver/palladium alloy that is, the "ion radius ratio” is 0.96 or more and 1.10 or less.
  • the addition ratio of (Ag 0.7 , Pd 0.3 )TiO 3 , NaTiO 3 and EuTiO 3 is not necessarily 100%, but if it is 10% or more, (Ag 0.7 , Pd 0.3 ) The effect of improving coverage was observed compared to the case where none of TiO 3 , NaTiO 3 and EuTiO 3 was included.
  • the ratio of the ionic radius of Ca in 6-coordination to the ionic radius of silver/palladium alloy in 6-coordination that is, the "ionic radius ratio” is 0.94. Therefore, the "ion radius ratio” was outside the range of 0.96 or more and 1.10 or less, and the coverage was as low as 72%.
  • SrTiO 3 Main component of ceramic constituting dielectric layer: SrTiO 3 1.
  • SrTiO 3 -based ceramic raw material constituting the dielectric layer As starting materials, the main component SrCO 3 and TiO 2 powders and the subcomponent MnO, SiO 2 and MgO powders were weighed and heated in a ball mill for 72 hours. After mixing, the mixture was heat-treated at a top temperature of 1000° C. for 2 hours to obtain SrTiO 3 ceramic raw material powder.
  • the conductive paste for forming internal electrodes contained the "ABO trioxide " powder shown in Table 4 below and the SrTiO 3 -based ceramic raw material powder for the dielectric layer. It was used as a ceramic powder.
  • Table 4 shows "ion radius ratio (A site element/Ag 0.7 Pd 0.3 alloy)" as in Table 2.
  • Table 4 shows "ion radius ratio (A site element/Ag 0.7 Pd 0.3 alloy)" as in Table 2.
  • Multilayer Ceramic Capacitor A ceramic slurry containing the SrTiO 3 ceramic raw material powder prepared in 1 above was prepared, and then a doctor blade method was applied to the ceramic slurry to form a ceramic green sheet. Thereafter, a multilayer ceramic capacitor serving as a sample was manufactured through the same steps as in Experimental Example 1.
  • Samples 21 to 26 in Table 4 have an “evaluation” of “ ⁇ ”.
  • the internal electrode contains one of (Ag 0.7 , Pd 0.3 )TiO 3 , NaTiO 3 and EuTiO 3 as an ABO 3 oxide.
  • the internal electrode contains a silver/palladium alloy as a conductive component.
  • the ionic radius of the silver/palladium alloy in six coordinations is 1.06 ⁇ .
  • the ionic radii of the A - site elements of (Ag 0.7 , Pd 0.3 )TiO 3 , NaTiO 3 and EuTiO 3 as ABO trioxides contained in the internal electrodes in Samples 21 to 26 in the 6-coordination are as shown in Table 1. 1, they are 1.06 ⁇ , 1.02 ⁇ and 1.17 ⁇ , respectively.
  • the ratio of the ionic radius of the element at the A site in ABO 3 in the 6-coordination to the ionic radius in the 6-coordination of the silver/palladium alloy that is, the "ion radius ratio” is 0.96 or more and 1.10 or less.
  • the ratio of the ionic radius of Sr in six coordinations to the ionic radius of silver/palladium alloy in six coordinations is 1.11. Therefore, the "ion radius ratio” was outside the range of 0.96 or more and 1.10 or less, and the coverage was as low as 70%.
  • Embodiments of this invention include the following.
  • a laminate comprising a plurality of laminated dielectric layers made of ceramic and a plurality of internal electrodes respectively arranged along the plurality of interfaces between the dielectric layers,
  • the internal electrode contains a silver/palladium alloy as a conductive component, and also contains at least one selected from (Ag 0.7 , Pd 0.3 )TiO 3 , NaTiO 3 and EuTiO 3 .
  • Multilayer ceramic capacitor Multilayer ceramic capacitor.
  • ⁇ 2> The multilayer ceramic capacitor according to ⁇ 1>, wherein the internal electrode has a thickness of 1 ⁇ m or less.
  • ⁇ 3> The multilayer ceramic capacitor according to ⁇ 1> or ⁇ 2>, wherein the internal electrode has a coverage of 80% or more.
  • the dielectric layer is made of ceramic containing at least one selected from BaTiO 3 , SrTiO 3 and CaZrO 3 as a main component
  • the internal electrode is made of ceramic containing at least one selected from BaTiO 3 , SrTiO 3 and CaZrO 3 contained in the dielectric layer.
  • the multilayer ceramic capacitor according to any one of ⁇ 1> to ⁇ 3>, further comprising at least one selected type.

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  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Ceramic Capacitors (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
PCT/JP2023/017695 2022-06-26 2023-05-11 積層セラミックコンデンサ Ceased WO2024004393A1 (ja)

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JP2024530347A JP7711847B2 (ja) 2022-06-26 2023-05-11 積層セラミックコンデンサ
US18/608,997 US20240222015A1 (en) 2022-06-26 2024-03-19 Multilayer ceramic capacitor

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JPH05304043A (ja) * 1992-04-27 1993-11-16 Toshiba Corp 導体形成用貴金属系組成物
JPH0645183A (ja) * 1992-07-21 1994-02-18 Matsushita Electric Ind Co Ltd パラジウムペーストおよび積層チップコンデンサの製造方法
JPH07192528A (ja) * 1993-12-27 1995-07-28 Nec Corp 導電性ペースト
JP2008103522A (ja) * 2006-10-19 2008-05-01 Nec Tokin Corp 積層セラミック部品用導電性ペーストおよびその製造方法
JP2020202245A (ja) * 2019-06-07 2020-12-17 太陽誘電株式会社 セラミック電子部品の製造方法

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US6027826A (en) * 1994-06-16 2000-02-22 The United States Of America As Represented By The Secretary Of The Air Force Method for making ceramic-metal composites and the resulting composites
WO2006046597A1 (ja) * 2004-10-26 2006-05-04 Murata Manufacturing Co., Ltd 導電性ペースト、及び積層型圧電セラミック部品
JP2016031807A (ja) 2014-07-28 2016-03-07 住友金属鉱山株式会社 導電性ペースト及びその製造方法
JP6387871B2 (ja) * 2015-03-13 2018-09-12 Tdk株式会社 誘電体磁器組成物およびセラミック電子部品
JP7441120B2 (ja) * 2020-06-05 2024-02-29 太陽誘電株式会社 積層セラミックコンデンサおよび誘電体材料
JP7591411B2 (ja) * 2021-01-13 2024-11-28 太陽誘電株式会社 誘電体およびセラミック電子部品

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05304043A (ja) * 1992-04-27 1993-11-16 Toshiba Corp 導体形成用貴金属系組成物
JPH0645183A (ja) * 1992-07-21 1994-02-18 Matsushita Electric Ind Co Ltd パラジウムペーストおよび積層チップコンデンサの製造方法
JPH07192528A (ja) * 1993-12-27 1995-07-28 Nec Corp 導電性ペースト
JP2008103522A (ja) * 2006-10-19 2008-05-01 Nec Tokin Corp 積層セラミック部品用導電性ペーストおよびその製造方法
JP2020202245A (ja) * 2019-06-07 2020-12-17 太陽誘電株式会社 セラミック電子部品の製造方法

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JP7711847B2 (ja) 2025-07-23
KR20250002677A (ko) 2025-01-07

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