WO2024004394A1 - 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

Info

Publication number
WO2024004394A1
WO2024004394A1 PCT/JP2023/017696 JP2023017696W WO2024004394A1 WO 2024004394 A1 WO2024004394 A1 WO 2024004394A1 JP 2023017696 W JP2023017696 W JP 2023017696W WO 2024004394 A1 WO2024004394 A1 WO 2024004394A1
Authority
WO
WIPO (PCT)
Prior art keywords
ceramic
internal electrode
internal electrodes
ceramic capacitor
multilayer ceramic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/017696
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
隆志 大原
英靖 大西
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Murata Manufacturing Co Ltd
Original Assignee
Murata Manufacturing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Murata Manufacturing Co Ltd filed Critical Murata Manufacturing Co Ltd
Priority to KR1020247039517A priority Critical patent/KR20250002675A/ko
Priority to JP2024530348A priority patent/JP7635889B2/ja
Priority to CN202380028707.0A priority patent/CN118901112A/zh
Publication of WO2024004394A1 publication Critical patent/WO2024004394A1/ja
Priority to US18/608,994 priority patent/US12412700B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/005—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
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • 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
    • 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
    • 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
    • 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
    • H01G4/228—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
    • 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 typically 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 achieved.
  • 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 present invention is characterized in that the internal electrode contains at least one selected from CuTiO 3 , CoTiO 3 and CrTiO 3 .
  • At least one selected from CuTiO 3 , CoTiO 3 and CrTiO 3 contained in the internal electrode contributes to increasing the coverage of the internal electrode. 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 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.
  • the internal electrodes 4 and 5 contain copper as a conductive component. Further, as a characteristic composition, the internal electrodes 4 and 5 contain at least one selected from CuTiO 3 , CoTiO 3 and CrTiO 3 . CuTiO 3 , CoTiO 3 and CrTiO 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 , and the internal electrodes 4 and 5 contains copper as a conductive component, contains at least one selected from CuTiO 3 , CoTiO 3 and CrTiO 3 as a ceramic material, and optionally contains BaTiO 3 , SrTiO 3 and CaZrO contained in the dielectric layer 3. It further contains at least one species selected from 3 .
  • 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 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.
  • 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 copper or an alloy thereof 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.
  • (Experimental example 1) Main component of ceramic constituting dielectric layer: BaTiO 3 1.
  • 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.
  • 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).
  • 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 included 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 CuTiO 3 , CoTiO 3 and CrTiO 3 as the ABO 3 oxide. Further, the internal electrode contains copper as a conductive component.
  • the ionic radius of copper in 6-coordination is 0.77 ⁇ .
  • the ionic radius of the A-site element of each of CuTiO 3 , CoTiO 3 and CrTiO 3 as ABO 3 oxides contained in the internal electrodes in Samples 1 to 6 in the 6-coordination is as follows. , 0.77 ⁇ , 0.74 ⁇ and 0.80 ⁇ .
  • 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 metal element contained in the conductive metal particles That is, the "ion radius ratio” is 0.96 or more and 1.04 or less.
  • CuTiO 3 , CoTiO 3 and CrTiO 3 as ABO 3 oxides in Samples 1 to 6 have the ionic radius of the 6-coordination of the A-site element in ABO 3 as the conductivity that should be included in the internal electrode. Since the ionic radius is equal to or close to the 6-coordination ionic radius of copper as a metal, the energy difference with the copper in the internal electrode is 0 or small, so it remains without being expelled from the internal electrode, and the heat resistance of the internal electrode is reduced. It acts to improve. As a result, it is estimated that the coverage of Samples 1 to 6 was as high as 84% or more.
  • the addition ratio of CuTiO 3 , CoTiO 3 and CrTiO 3 is not necessarily 100%, but if it is 10% or more, none of CuTiO 3 , CoTiO 3 and CrTiO 3 is included.
  • the effect of improving coverage was observed compared to the previous case.
  • the coverage of samples 4 to 6 in which the addition ratio of CuTiO 3 , CoTiO 3 and CrTiO 3 was 10% was equal to the coverage of samples 1 to 3 in which the addition ratio was 100%. It is also noteworthy that there are
  • the ratio of the ionic radius of Ba in 6-coordination to the ionic radius of copper in 6-coordination that is, the "ion radius ratio” is 1.75. Therefore, the "ion radius ratio” was outside the range of 0.96 or more and 1.04 or less, and the coverage was as low as 74%.
  • 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 the "ion radius ratio (A-site element/metallic copper)".
  • the ratio of the ionic radius (1.00 ⁇ ) of the Ca element in the 6-coordination shown in Table 1 to the ionic radius (0.77 ⁇ ) of copper in the 6-coordination is shown. .
  • 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 CuTiO 3 , CoTiO 3 and CrTiO 3 as the ABO 3 oxide. Further, the internal electrode contains copper as a conductive component.
  • the ionic radius of copper in 6-coordination is 0.77 ⁇ .
  • the ionic radii of the A-site elements of CuTiO 3 , CoTiO 3 and CrTiO 3 as the ABO 3 oxides contained in the internal electrodes of Samples 11 to 16 are as shown in Table 1. , 0.77 ⁇ , 0.74 ⁇ and 0.80 ⁇ .
  • CuTiO 3 , CoTiO 3 and CrTiO 3 as ABO 3 oxides in Samples 11 to 16 have the ionic radius of the 6-coordination of the A-site element in ABO 3 as the conductivity that should be included in the internal electrode. Since the ionic radius is equal to or close to the 6-coordination ionic radius of copper as a metal, the energy difference with the copper in the internal electrode is 0 or small, so it remains without being expelled from the internal electrode, and the heat resistance of the internal electrode is improved. It is presumed that as a result, the coverage of Samples 11 to 16 was as high as 81% or more.
  • the addition ratio of CuTiO 3 , CoTiO 3 and CrTiO 3 is not necessarily 100%, but if it is 10% or more, none of CuTiO 3 , CoTiO 3 and CrTiO 3 is included. The effect of improving coverage was observed compared to the previous case.
  • 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/metallic copper)" as in Table 2.
  • Table 4 shows "ion radius ratio (A site element/metallic copper)" as in Table 2.
  • the ratio of the ionic radius (1.18 ⁇ ) of the Sr element in the 6-coordination shown in Table 1 to the ionic radius (0.77 ⁇ ) in the 6-coordination of copper is shown. .
  • 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 CuTiO 3 , CoTiO 3 and CrTiO 3 as the ABO 3 oxide. Further, the internal electrode contains copper as a conductive component.
  • the ionic radius of copper in 6-coordination is 0.77 ⁇ .
  • the ionic radii of the A-site elements of CuTiO 3 , CoTiO 3 and CrTiO 3 as the ABO 3 oxides contained in the internal electrodes of Samples 21 to 26 are as follows: , 0.77 ⁇ , 0.74 ⁇ and 0.80 ⁇ .
  • CuTiO 3 , CoTiO 3 and CrTiO 3 as ABO 3 oxides in Samples 21 to 26 have an ionic radius of the 6-coordination of the A-site element in ABO 3 , which is the conductivity that should be included in the internal electrode. Since the ionic radius is equal to or close to the 6-coordination ionic radius of copper as a metal, the energy difference with the copper in the internal electrode is 0 or small, so it remains without being expelled from the internal electrode, and the heat resistance of the internal electrode is improved. It is presumed that as a result, the coverage of Samples 21 to 26 was as high as 80% or more.
  • the addition ratio of CuTiO 3 , CoTiO 3 and CrTiO 3 is not necessarily 100%, but if it is 10% or more, none of CuTiO 3 , CoTiO 3 and CrTiO 3 is included. The effect of improving coverage was observed compared to the previous case.
  • the "ion radius ratio" was outside the range of 0.96 or more and 1.04 or less, and SrTiO 3 was discharged from the internal electrode portion, which did not improve the heat resistance of the internal electrode and resulted in low coverage. It is assumed that it was
  • the ionic radius in the 6-coordination of the conductive metal element contained in the internal electrode is (1/1.04) of the ionic radius in the 6-coordination of the A-site element in CuTiO 3 , CoTiO 3 and CrTiO 3 .
  • Metals other than copper may be used as the conductive metal included in the internal electrodes, as long as the relationship of the above and (1/0.96) or less is satisfied.
  • 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 at least one selected from CuTiO 3 , CoTiO 3 and CrTiO 3 .
  • Multilayer ceramic capacitor Multilayer ceramic capacitor.
  • ⁇ 3> The multilayer ceramic capacitor according to ⁇ 1> or ⁇ 2>, wherein the internal electrode has a thickness of 1 ⁇ m or less.
  • ⁇ 4> The multilayer ceramic capacitor according to any one of ⁇ 1> to ⁇ 3>, wherein the internal electrode has a coverage of 80% or more.

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Ceramic Capacitors (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
PCT/JP2023/017696 2022-06-26 2023-05-11 積層セラミックコンデンサ Ceased WO2024004394A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020247039517A KR20250002675A (ko) 2022-06-26 2023-05-11 적층 세라믹 콘덴서
JP2024530348A JP7635889B2 (ja) 2022-06-26 2023-05-11 積層セラミックコンデンサ
CN202380028707.0A CN118901112A (zh) 2022-06-26 2023-05-11 层叠陶瓷电容器
US18/608,994 US12412700B2 (en) 2022-06-26 2024-03-19 Multilayer ceramic capacitor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022102290 2022-06-26
JP2022-102290 2022-06-26

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US18/608,994 Continuation US12412700B2 (en) 2022-06-26 2024-03-19 Multilayer ceramic capacitor

Publications (1)

Publication Number Publication Date
WO2024004394A1 true WO2024004394A1 (ja) 2024-01-04

Family

ID=89381971

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/017696 Ceased WO2024004394A1 (ja) 2022-06-26 2023-05-11 積層セラミックコンデンサ

Country Status (5)

Country Link
US (1) US12412700B2 (https=)
JP (1) JP7635889B2 (https=)
KR (1) KR20250002675A (https=)
CN (1) CN118901112A (https=)
WO (1) WO2024004394A1 (https=)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4956822A (https=) * 1972-06-30 1974-06-03
JP2001284162A (ja) * 2000-03-31 2001-10-12 Kyocera Corp 導電性ペーストおよび積層型電子部品並びにその製法
JP2013214698A (ja) * 2012-04-02 2013-10-17 Samsung Electro-Mechanics Co Ltd 内部電極用導電性ペースト組成物及びそれを含む積層セラミック電子部品
JP2015083714A (ja) * 2013-09-18 2015-04-30 株式会社村田製作所 複合粉末の製造方法およびこの製造方法により得られた複合粉末を用いた導電性厚膜ペーストおよび積層セラミック電子部品

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3877214B2 (ja) 2003-09-30 2007-02-07 Ｔｄｋ株式会社 積層型電子部品および積層型電子部品の製造方法
US7544314B2 (en) * 2004-09-01 2009-06-09 Tdk Corporation Glass composition for thick film resistor paste, thick film resistor paste, thick-film resistor, and electronic device
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
JP6437270B2 (ja) 2014-10-21 2018-12-12 株式会社クラレ ビニルアセタール系重合体樹脂組成物並びにそれを用いたフィルム、セラミックグリーンシート及び積層体
JP6823976B2 (ja) 2016-09-06 2021-02-03 太陽誘電株式会社 積層セラミックコンデンサおよびその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4956822A (https=) * 1972-06-30 1974-06-03
JP2001284162A (ja) * 2000-03-31 2001-10-12 Kyocera Corp 導電性ペーストおよび積層型電子部品並びにその製法
JP2013214698A (ja) * 2012-04-02 2013-10-17 Samsung Electro-Mechanics Co Ltd 内部電極用導電性ペースト組成物及びそれを含む積層セラミック電子部品
JP2015083714A (ja) * 2013-09-18 2015-04-30 株式会社村田製作所 複合粉末の製造方法およびこの製造方法により得られた複合粉末を用いた導電性厚膜ペーストおよび積層セラミック電子部品

Also Published As

Publication number Publication date
US20240222014A1 (en) 2024-07-04
JP7635889B2 (ja) 2025-02-26
US12412700B2 (en) 2025-09-09
CN118901112A (zh) 2024-11-05
KR20250002675A (ko) 2025-01-07
JPWO2024004394A1 (https=) 2024-01-04

Similar Documents

Publication Publication Date Title
JP7813394B2 (ja) 積層型電子部品及びその製造方法
US12437919B2 (en) Multilayer ceramic capacitor
WO2024004394A1 (ja) 積層セラミックコンデンサ
JP7635888B2 (ja) 導電性ペースト
JP7597236B2 (ja) 導電性ペースト
WO2024004392A1 (ja) 積層セラミックコンデンサ
WO2024004393A1 (ja) 積層セラミックコンデンサ
JP2024003265A (ja) 導電性ペースト
JP2024003266A (ja) 導電性ペースト
KR102955824B1 (ko) 적층 세라믹 콘덴서
WO2024181021A1 (ja) 積層セラミックコンデンサ

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23830846

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2024530348

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 202380028707.0

Country of ref document: CN

ENP Entry into the national phase

Ref document number: 20247039517

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1020247039517

Country of ref document: KR

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 23830846

Country of ref document: EP

Kind code of ref document: A1