WO2023053676A1 - 導電性ペースト - Google Patents

導電性ペースト Download PDF

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Publication number
WO2023053676A1
WO2023053676A1 PCT/JP2022/027954 JP2022027954W WO2023053676A1 WO 2023053676 A1 WO2023053676 A1 WO 2023053676A1 JP 2022027954 W JP2022027954 W JP 2022027954W WO 2023053676 A1 WO2023053676 A1 WO 2023053676A1
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Prior art keywords
powder
conductive paste
ceramic
ionic radius
internal electrodes
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PCT/JP2022/027954
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English (en)
French (fr)
Japanese (ja)
Inventor
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 JP2023550402A priority Critical patent/JP7597236B2/ja
Priority to CN202280047085.1A priority patent/CN117597753A/zh
Priority to KR1020247004800A priority patent/KR102935374B1/ko
Publication of WO2023053676A1 publication Critical patent/WO2023053676A1/ja
Priority to US18/598,301 priority patent/US12469641B2/en
Anticipated expiration legal-status Critical
Priority to US19/357,484 priority patent/US20260038737A1/en
Ceased legal-status Critical Current

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/12—Metallic powder containing non-metallic particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0433—Nickel- or cobalt-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • 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
    • H01G4/0085—Fried 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
    • H01G4/005—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
    • H01G4/228—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/15—Nickel or cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/25—Oxide
    • 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 conductive paste, and more particularly to a conductive paste for forming internal electrodes of laminated ceramic capacitors.
  • a multilayer ceramic capacitor usually has a plurality of laminated dielectric layers made of ceramic and a plurality of internal electrodes arranged along a plurality of interfaces between the dielectric layers. and a plurality of external electrodes provided on the external 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 alternately arranged in the stacking direction of the laminate, and the external electrode is a first external electrode electrically connected to the first internal electrode. an 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 to be the internal electrodes are sintered is higher than the temperature at which the ceramic constituting the dielectric layers is sintered. is low, the metal particles contained in the internal electrodes are sintered first. This causes a reduction in the coverage of the internal electrodes.
  • internal electrodes having a thickness of 1 ⁇ m or less, for example, tend to have reduced coverage.
  • the temperature at which the conductive metal particles contained in the conductive paste film to be the internal electrodes are sintered in the firing process during the manufacture of the multilayer ceramic capacitor is required. needs to be higher.
  • the temperature at which the metal particles contained in the conductive paste film to be the internal electrodes are sintered can be brought close to the temperature at which the ceramics constituting the dielectric layers start to be sintered.
  • the shrinkage timing during sintering can be brought closer between. As a result, the coverage of the internal electrodes is increased, and a large capacity can be achieved.
  • an internal electrode forming method is used. It is known to add a ceramic material having a composition similar to that of the ceramic constituting the dielectric layer, that is, a common material, to the conductive paste. By adding the common material, the sintering timing of the metal particles contained in the conductive paste film to be the internal electrode can be shifted to a higher temperature side, and the metal particles contained in the conductive paste film are sintered. The temperature can approach the temperature at which the ceramic that makes up the dielectric layer will sinter.
  • the temperature at which the metal particles contained in the conductive paste are sintered is still lower than the temperature at which the ceramic constituting the dielectric layer is sintered. It is undeniably low, and further improvement is desired.
  • the present invention has been made in view of such problems, and an object thereof is to provide a conductive paste for forming internal electrodes, which can maintain a relatively high coverage even when the internal electrodes are thinned.
  • the present invention provides a conductive paste for forming internal electrodes of a multilayer ceramic capacitor containing conductive metal powder, ceramic powder, an organic solvent and an organic binder.
  • the ratio of the ionic radius of the six-coordinated element of the A site in ABO3 to the ionic radius of the six-coordinated metal element contained in the conductive metal powder is 0.97 or more and 1.04 or less. It is characterized by being a powder composed of an ABO 3 type oxide with a specific ion radius.
  • the coverage of the internal electrodes can be increased. Therefore, even if the thickness of the internal electrodes is reduced, high coverage of the internal electrodes can be maintained, and the increase in capacity of the multilayer ceramic capacitor can be prevented.
  • FIG. 1 is a cross-sectional view schematically showing a laminated ceramic capacitor 1 to which a conductive paste according to the present invention is applied;
  • the multilayer ceramic capacitor 1 includes a laminate 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 interfaces 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 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 laminated body 2, more specifically, on each end face facing each other.
  • the first external electrode 6 is electrically connected to the first internal electrode 4 and the second external electrode 7 is electrically connected to the second internal electrode 5 .
  • the dielectric layer 3 is made of a ceramic mainly composed of, for example, ABO 3 (A is at least one of Ba, Ca and Sr, and B is at least one of Ti and Zr). Become.
  • the ceramic may contain ABO 3 as a main component and at least one of Mn, Mg, Si, Y, Dy and Gd as an accessory component.
  • the internal electrodes 4 and 5 preferably contain Ni as a conductive component. Furthermore, as a characteristic composition, the internal electrodes 4 and 5 contain at least one selected from NiTiO 3 , MgTiO 3 and MnTiO 3 . NiTiO 3 , MgTiO 3 and MnTiO 3 have an ilmenite crystal structure.
  • the dielectric layer 3 is made of a ceramic containing at least one selected from BaTiO 3 , SrTiO 3 and CaZrO 3 as a main component, and the internal electrodes 4 and 5 contains nickel as a conductive component, contains at least one selected from NiTiO 3 , MgTiO 3 and MnTiO 3 as a ceramic material, and if necessary BaTiO 3 , SrTiO 3 and CaZrO contained in the dielectric layer 3 At least one selected from 3 is further included.
  • the external electrodes 6 and 7 are formed, for example, by applying a conductive paste containing Ag or Cu as the main conductive component to the end face of the laminate 2 and baking it. If necessary, the thick film formed by baking may be plated with, for example, Ni plating and Sn plating thereon.
  • the multilayer ceramic capacitor 1 is manufactured through the following steps, for example. First, a ceramic slurry containing raw ceramic powder having the composition as described above is prepared. Next, an appropriate sheet forming method is applied to the ceramic slurry to form a ceramic green sheet. Next, a conductive paste to be each of the internal electrodes 4 and 5 is applied by printing or the like onto predetermined ceramic green sheets among the plurality of ceramic green sheets. Next, after laminating a plurality of ceramic green sheets, they are pressure-bonded to obtain a green laminate. The green laminate is then fired. The ceramic green sheet becomes the dielectric layer 3 in this firing step. After that, external electrodes 6 and 7 are formed on the end surfaces of the laminate 3 .
  • the conductive paste to be the internal electrodes 4 and 5 used in manufacturing the multilayer ceramic capacitor 1 described above is preferably prepared as follows.
  • ceramic powder slurry is prepared by mixing ceramic powder and a dispersant in an organic solvent.
  • the ceramic powder for example, one made of at least one selected from NiTiO 3 , MgTiO 3 and MnTiO 3 as ABO 3 oxides is used. 3 and CaZrO 3 may be used.
  • the conductive metal powder contained in the metal powder slurry prepared in the second step described later contains nickel, NiTiO 3 , MgTiO 3 and MnTiO 3 as the above-mentioned ABO 3 oxides are six-coordinated nickel elements.
  • the ratio of the ionic radius of the six-coordinated element of the A site in ABO3 to the ionic radius of ABO3 is 0.97 or more and 1.04 or less.
  • the conductive metal powder contained in the metal powder slurry produced in the second step and the possible reaction between The ceramic powder contains the above ABO 3 oxide as a main component and may further contain at least one of Mn, Mg, Si, Y, Dy and Gd as an accessory component. When such subcomponents are contained, grain growth of ceramic particles is suppressed, and sintering of metal particles can be effectively suppressed.
  • An anionic polymer dispersant for example, can be used as the dispersant mixed with the ceramic powder in the first step, and dihydroterpineol, for example, can be used as the organic solvent.
  • a metal powder slurry is prepared by mixing a conductive metal powder and a dispersing agent in an organic solvent.
  • a conductive metal powder for example, a powder made of metallic nickel or an alloy thereof is used.
  • the dispersant and organic solvent used in the second step the same dispersant and organic solvent as those used in the first step can be used.
  • an organic vehicle is produced by mixing an organic resin component with an organic solvent.
  • an organic solvent for example, ethyl cellulose resin can be used as the organic resin component.
  • the organic solvent used in the third step the same organic solvent as used in the first step can be used.
  • the ceramic powder slurry, the metal powder slurry and the organic vehicle are mixed.
  • a conductive paste to be the internal electrodes 4 and 5 is thus obtained.
  • This conductive paste contains a ceramic powder slurry, and the ceramic powder slurry consists of at least one selected from NiTiO 3 , MgTiO 3 and MnTiO 3 as ABO 3 oxides with specific ionic radii as described above. Therefore, the internal electrodes 4 and 5 provided in the multilayer ceramic capacitor 1 manufactured through the firing process contain at least one selected from NiTiO 3 , MgTiO 3 and MnTiO 3 .
  • nickel powder was prepared as the conductive metal powder contained in the conductive paste for forming internal electrodes.
  • NiTiO 3 , MgTiO 3 and MnTiO 3 , CuTiO 3 , BaTiO 3 , CaZrO 3 and SrTiO 3 were used as ABO 3 oxides with specific ionic radii constituting the ceramic powder contained in the conductive paste for forming internal electrodes.
  • Table 1 shows the "crystal structure", “coordination number”, "A-site element” and "ionic radius” for these ABO 3 oxides.
  • Ba, Ca, and Sr are 12-coordinated in the original perovskite structure, but Ba, Ca, and Sr also dissolve in sites of 6-coordinated elements (Ni, Mg, Mn) in the ilmenite structure. Since the number of coordinates is 6, the "ionic radius" in Table 1 indicates the value for the 6-coordination.
  • (Experimental example 1) Main component of ceramic constituting dielectric layer: BaTiO3 1.
  • Preparation of BaTiO 3 -Based Ceramic Raw Materials Constituting Dielectric Layers As starting raw materials, powders of the main components BaCO 3 and TiO 2 were weighed and mixed in a ball mill for 72 hours, followed by heat treatment at a top temperature of 1000° C. for 2 hours. A heat treated powder was obtained.
  • powders of MnO , Dy 2 O 3 , MgO, SiO 2 and BaCO 3 were prepared as subcomponent powders. These auxiliary component powders were added to the heat-treated powder, mixed for 24 hours by a ball mill, and then dried to obtain a BaTiO 3 ceramic raw material powder.
  • ABO 3 oxide powder and BaTiO 3 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.
  • a ceramic powder slurry was prepared by pre-mixing with a system polymer dispersant in a non-medium agitating mill, followed by dispersion treatment in a medium agitating mill (first step).
  • nickel powder as a conductive metal powder, dihydroterpineol as an organic solvent, and an anionic polymer dispersant as a dispersant were dispersed in a three-roll mill to prepare a metal powder slurry (second process).
  • the metal powder slurry and the ceramic powder slurry were added to the organic vehicle and mixed and dispersed to prepare a conductive paste for forming internal electrodes (fourth step).
  • Table 2 shows the ratio of the ionic radius of the A-site element at 6-coordination to the ionic radius at 6-coordination of nickel to be contained in the internal electrode, that is, "ionic radius ratio (A-site element/metallic nickel) "It is shown.
  • ionic radius ratio A-site element/metallic nickel
  • the internal electrode and the dielectric layer located at the center in the height direction of the laminate provided in the sample multilayer ceramic capacitor were peeled off from each other by electric field peeling.
  • NiTiO 3 the ionic radius of the six-coordinated nickel is 0.69 ⁇ .
  • Table 1 shows the ionic radii of NiTiO 3 , MgTiO 3 and MnTiO 3 as ABO 3 oxides contained in the internal electrodes of Samples 1 to 3 and 5 to 7 at the six-coordinate A-site element. 0.69 ⁇ , 0.72 ⁇ and 0.67 ⁇ , respectively.
  • the ionic radius of the 6-coordinated element of the metal element contained in the conductive metal particles is The ratio of radii, that is, the "ion radius ratio” is 0.97 or more and 1.04 or less.
  • NiTiO 3 , MgTiO 3 and MnTiO 3 as ABO 3 oxides in samples 1 to 3 and 5 to 7 have ionic radii at 6-coordination of the A-site element in ABO 3 contained in the internal electrodes. Since it is equal to or close to the ionic radius of the six-coordinated nickel as a conductive metal to be used, the energy difference with nickel in the internal electrode is 0 or small, so that it remains without being discharged from the internal electrode portion, and the internal It acts to improve the heat resistance of the electrode. As a result, samples 1-3 and 5-7 are presumed to have a high coverage of 84% or more.
  • the addition ratio of NiTiO 3 , MgTiO 3 and MnTiO 3 is not necessarily 100%, and if it is 10% or more, none of NiTiO 3 , MgTiO 3 and MnTiO 3 is included. The effect of improving the coverage was recognized as compared with the case. Note that in Experimental Example 1, the coverage of samples 5 to 7 in which the addition ratio of NiTiO 3 , MgTiO 3 and MnTiO 3 is 10% shows the same value as the coverage of samples 1 to 3 in which the addition ratio is 100%. It is also noted that
  • the "ionic radius ratio" was out of the range of 0.97 or more and 1.04 or less, respectively, CuTiO 3 and BaTiO 3 were discharged from the internal electrode portion, and the heat resistance of the internal electrode was deteriorated. It is presumed that the coverage did not improve and the coverage became low.
  • Table 3 shows the "ion radius ratio (A-site element/metallic nickel)".
  • the ratio of the ionic radius (1.00 ⁇ ) of Ca at 6-coordination shown in Table 1 to the ionic radius (0.69 ⁇ ) of Ni at 6-coordination is shown.
  • Multilayer Ceramic Capacitor A ceramic slurry containing the CaZrO 3 -based ceramic raw material powder prepared in 1 above was prepared, and then a doctor blade method was applied to the ceramic slurry to form ceramic green sheets. Thereafter, through the same steps as in Experimental Example 1, a multilayer ceramic capacitor was produced as a sample.
  • Samples 11 to 13 and 15 to 17 in Table 3 are evaluated as " ⁇ ".
  • the internal electrodes contained any of NiTiO 3 , MgTiO 3 and MnTiO 3 as ABO 3 oxide.
  • the internal electrode contains nickel as a conductive component.
  • NiTiO 3 the ionic radius of the six-coordinated nickel is 0.69 ⁇ .
  • Table 1 shows the ionic radii of NiTiO 3 , MgTiO 3 and MnTiO 3 as the ABO 3 oxides contained in the internal electrodes of Samples 11 to 13 and 15 to 17 at the six-coordinate A-site element. 0.69 ⁇ , 0.72 ⁇ and 0.67 ⁇ , respectively.
  • NiTiO 3 , MgTiO 3 and MnTiO 3 as ABO 3 oxides in samples 11 to 13 and 15 to 17 have ionic radii at the six-coordinated A-site elements in ABO 3 , which are contained in the internal electrodes. Since it is equal to or close to the ionic radius of the six-coordinated nickel as a conductive metal to be used, the energy difference with nickel in the internal electrode is 0 or small, so that it remains without being discharged from the internal electrode portion, and the internal It is presumed that this acted to improve the heat resistance of the electrode, and as a result, the coverage was as high as 81% or more in samples 11-13 and 15-17.
  • the addition ratio of NiTiO 3 , MgTiO 3 and MnTiO 3 is not necessarily 100%, and if it is 10% or more, none of NiTiO 3 , MgTiO 3 and MnTiO 3 is included. The effect of improving the coverage was recognized as compared with the case.
  • the "ionic radius ratio" was out of the range of 0.97 or more and 1.04 or less, respectively, CuTiO 3 and CaZrO 3 were discharged from the internal electrode portion, and the heat resistance of the internal electrode was deteriorated. It is presumed that the coverage did not improve and the coverage became low.
  • Table 4 shows the "ionic radius ratio (A-site element/metallic nickel)".
  • the ratio of the ionic radius (1.18 ⁇ ) for six-coordinated Sr shown in Table 1 to the ionic radius (0.69 ⁇ ) for six-coordinated Ni 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 ceramic green sheets. Thereafter, through the same steps as in Experimental Example 1, a multilayer ceramic capacitor was produced as a sample.
  • Samples 21 to 23 and 25 to 27 in Table 4 have an "evaluation" of " ⁇ ".
  • the internal electrodes contained any of NiTiO 3 , MgTiO 3 and MnTiO 3 as ABO 3 oxide.
  • the internal electrode contains nickel as a conductive component.
  • NiTiO 3 the ionic radius of the six-coordinated nickel is 0.69 ⁇ .
  • Table 1 shows the ionic radii of NiTiO 3 , MgTiO 3 and MnTiO 3 as the ABO 3 oxides contained in the internal electrodes of Samples 21 to 23 and 25 to 27 at the six-coordinate A-site element. 0.69 ⁇ , 0.72 ⁇ and 0.67 ⁇ , respectively.
  • NiTiO 3 , MgTiO 3 and MnTiO 3 as ABO 3 oxides in samples 21 to 23 and 25 to 27 have ionic radii at 6-coordination of the A-site elements in ABO 3 that are included in the internal electrodes. Since it is equal to or close to the ionic radius of the six-coordinated nickel as a conductive metal to be used, the energy difference with nickel in the internal electrode is 0 or small, so that it remains without being discharged from the internal electrode portion, and the internal It is presumed that this acted to improve the heat resistance of the electrode, and as a result, the coverage of samples 21-23 and 25-27 was as high as 80% or more.
  • the addition ratio of NiTiO 3 , MgTiO 3 and MnTiO 3 is not necessarily 100%, and if it is 10% or more, none of NiTiO 3 , MgTiO 3 and MnTiO 3 is included. The effect of improving the coverage was recognized as compared with the case.
  • sample 28 which was also evaluated as "x"
  • SrTiO 3 as a common material was added to the internal electrodes.
  • Sr which is an element at the A site in ABO3 of the perovskite structure, has 12 coordinates. It is necessary to compare the ionic radii at the 6-coordinated positions of Sr. Therefore, the ratio of the ionic radius of Sr with 6-coordinates to the ionic radius of nickel with 6-coordinates, that is, the "ionic radius ratio" is 1.71. Therefore, the "ionic radius ratio” was out of the range of 0.97 or more and 1.04 or less, and the coverage was as low as 70%.
  • the "ionic radius ratio" was out of the range of 0.97 or more and 1.04 or less, respectively, CuTiO 3 and SrTiO 3 were discharged from the internal electrode portion, and the heat resistance of the internal electrode was deteriorated. It is presumed that the coverage did not improve and the coverage became low.
  • nickel powder was used as the conductive metal powder contained in the conductive paste for forming internal electrodes. Since many commercially available multilayer ceramic capacitors use nickel as the conductive component of the internal electrodes, using nickel powder as the conductive metal powder contained in the conductive paste for forming the internal electrodes reduces design changes. It is advantageous in that it can be used as the conductive metal powder contained in the conductive paste for forming the internal electrodes. Since many commercially available multilayer ceramic capacitors use nickel as the conductive component of the internal electrodes, using nickel powder as the conductive metal powder contained in the conductive paste for forming the internal electrodes reduces design changes. It is advantageous in that it can
  • the powder composed of ABO3 -type oxide with a specific ionic radius as at least part of the ceramic powder contained in the conductive paste is other than at least one selected from NiTiO3 , MgTiO3 and MnTiO3 .
  • the ABO 3 -type oxide with a specific ionic radius is 6-coordinated to the 6-coordinated element of the A-site in ABO 3 with respect to the ionic radius of the 6-coordinated metal element contained in the conductive metal powder contained in the conductive paste.
  • Any ABO 3 type oxide may be used as long as the ratio of the ionic radii at is 0.97 or more and 1.04 or less.

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JP2000232032A (ja) * 1999-02-10 2000-08-22 Tdk Corp 電極形成用ニッケル複合導体及び積層セラミックコンデンサ

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US20260038737A1 (en) 2026-02-05
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