WO2023054378A1 - 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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Publication number
WO2023054378A1
WO2023054378A1 PCT/JP2022/035978 JP2022035978W WO2023054378A1 WO 2023054378 A1 WO2023054378 A1 WO 2023054378A1 JP 2022035978 W JP2022035978 W JP 2022035978W WO 2023054378 A1 WO2023054378 A1 WO 2023054378A1
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Prior art keywords
dielectric
particles
layer
inner layer
ceramic capacitor
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PCT/JP2022/035978
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English (en)
French (fr)
Japanese (ja)
Inventor
信弥 磯田
英之 橋本
優汰 大嶋
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to CN202280059867.7A priority Critical patent/CN117916833A/zh
Priority to JP2023551539A priority patent/JP7806805B2/ja
Priority to KR1020247009466A priority patent/KR102845978B1/ko
Publication of WO2023054378A1 publication Critical patent/WO2023054378A1/ja
Priority to US18/423,457 priority patent/US20240170220A1/en
Anticipated expiration legal-status Critical
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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
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
    • H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • 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
    • H01G4/005—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
    • 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
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • 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.
  • Multilayer ceramic capacitors have a structure in which dielectric layers and internal electrode layers are alternately laminated.
  • Multilayer ceramic capacitors using a variety of materials are known, but a low cost capacitor uses a barium titanate (BaTiO 3 ) compound for the dielectric layers and a base metal such as nickel (Ni) for the internal electrode layers. It is widely used because it is flexible and exhibits high characteristics.
  • Patent Document 1 a main component consisting of a perovskite compound represented by the composition formula (Ba 1-x-y Sr x Ca y ) m (Ti 1-z Zr z )O 3 and a rare earth element R a first subcomponent consisting of an oxide; a second subcomponent consisting of an oxide of Mg; a third subcomponent consisting of an oxide of at least one element M selected from Mn, Cr, Co and Fe; Regarding the dielectric porcelain composition containing the fourth subcomponent as a sintering aid, it is preferable to apply it to the dielectric layer of a laminated ceramic capacitor, and to use Ni or a Ni alloy as the conductive material contained in the internal electrode layers. (Claim 1, [0017] and [0039] of Patent Document 1).
  • the dielectric constant of the dielectric layer In order to realize miniaturization and large capacity of multilayer ceramic capacitors, it is important to increase the dielectric constant of the dielectric layer and promote its thinning.
  • the temperature change tends to increase. If the temperature change of the dielectric constant is large, the capacity temperature characteristic of the multilayer ceramic capacitor deteriorates. Further, if the thickness of the dielectric layer is reduced, the life of the insulation resistance between the internal electrode layers is shortened, leading to deterioration of reliability.
  • the conventional technique has a certain effect, there is a limit in obtaining a multilayer ceramic capacitor having a high dielectric constant, a flat temperature characteristic, and excellent reliability.
  • An object of the present invention is to provide a multilayer ceramic capacitor excellent in
  • the present invention includes the following aspects.
  • the expression "-" includes both numerical values. That is, "X to Y” is synonymous with “X or more and Y or less”.
  • the first main surface and second main surface facing each other in the thickness direction, the first side surface and second side surface facing each other in the width direction, and the first end surface and second side surface facing each other in the length direction a laminate having two end faces and including a plurality of dielectric layers and a plurality of internal electrode layers laminated in the thickness direction;
  • a multilayer ceramic capacitor comprising a pair of external electrodes connected to the layer, the dielectric layer comprises dielectric particles;
  • the laminate is a layered first side portion that extends along the first side surface and does not include an internal electrode layer; a layered second side portion that extends along the second side surface and does not include an internal electrode layer; a first outer layer portion sandwiched between the first side portion and the second side portion and sandwiched between the internal electrode layer closest to the first main surface and the first main surface; a second outer layer portion sandwiched between the first side portion and the second side portion and sandwiched between the second main surface and an internal electrode layer closest to the second main surface; Divided into an inner layer
  • the present invention it is possible to provide a multilayer ceramic capacitor that has a high dielectric constant, can be made smaller and has a larger capacity, has a flat temperature characteristic of the dielectric constant, and has excellent reliability.
  • FIG. 1 is a perspective view showing an outer shape of a laminated ceramic capacitor;
  • FIG. 1 is a cross-sectional view schematically showing the internal structure of a laminated ceramic capacitor;
  • FIG. 1 is a cross-sectional view schematically showing the internal structure of a laminated ceramic capacitor;
  • FIG. TEM-HAADF image showing particles with voids.
  • this embodiment A specific embodiment of the present invention (hereinafter referred to as “this embodiment") will be described.
  • the present invention is not limited to the following embodiments, and various modifications are possible within the scope of the present invention.
  • Laminated ceramic capacitor The laminated ceramic capacitor of the present embodiment has first and second main surfaces facing each other in the thickness direction, first and second side faces facing each other in the width direction, and facing each other in the length direction. It has a first end surface and a second end surface.
  • This multilayer ceramic capacitor includes a laminate including a plurality of dielectric layers and a plurality of internal electrode layers laminated in a thickness direction, and a plurality of internal electrode layers provided on each of the first end face and the second end face and connected to the plurality of internal electrode layers. and a pair of external electrodes.
  • the dielectric layer contains dielectric particles.
  • the laminate includes a layered first side portion that extends along the first side surface and does not include the internal electrode layer, and a layered second side portion that extends along the second side surface and does not include the internal electrode layer.
  • the dielectric layer at the center in the thickness direction of the inner layer section contains particles having voids as dielectric particles.
  • FIG. 1 is a perspective view showing the outline of a laminated ceramic capacitor.
  • 2 is a cross-sectional view of the laminated ceramic capacitor shown in FIG. 1 taken along line II-II
  • FIG. 3 is a cross-sectional view of the laminated ceramic capacitor shown in FIG. 1 taken along line III-III. .
  • a multilayer ceramic capacitor (100) comprises a laminate (6) including a plurality of laminated dielectric layers (2) and a plurality of internal electrode layers (4), and both end surfaces (14a, 14b) of the laminate (6). ), and a pair of external electrodes (8a, 8b) provided on the substrate.
  • a multilayer ceramic capacitor (100) and a laminate (6) have a substantially rectangular parallelepiped shape.
  • a substantially rectangular parallelepiped includes not only a rectangular parallelepiped but also a rectangular parallelepiped with rounded corners and/or ridges.
  • the corner portion is a portion where three surfaces of the laminate (6) intersect
  • the ridge portion is a portion where two surfaces of the laminate intersect.
  • the multilayer ceramic capacitor (100) and the laminate (6) have a rectangular parallelepiped shape with rounded corners and/or ridges.
  • the multilayer ceramic capacitor (100) and the laminate (6) have a first main surface (10a) and a second main surface (10b) facing in the thickness direction T, and a first side surface (12a) facing in the width direction W and It has a second side surface (12b) and longitudinally opposed first (14a) and second (14b) end surfaces.
  • the thickness direction T refers to the direction in which the dielectric layer (2) and the internal electrode layer (4) are laminated.
  • the length direction L is orthogonal to the thickness direction T and indicates the direction in which the end faces (14a, 14b) face each other.
  • the width direction W is a direction orthogonal to the thickness direction T and the length direction L. As shown in FIG.
  • a plane containing the thickness direction T and the width direction W is defined as the WT plane
  • a plane containing the width direction W and the length direction L is defined as the LW plane
  • a plane containing the length direction L and the thickness direction T is called the LT plane. defined as a surface.
  • the external electrodes (8a, 8b) include a first external electrode (8a) provided on the first end surface (14a) and a second external electrode (8b) provided on the second end surface (14b).
  • the first external electrode (8a) extends not only to the first end surface (14a) but also to one of the first main surface (10a), the second main surface (10b), the first side surface (12a) and the second side surface (12b). You can turn around to the department.
  • the second external electrode (8b) is formed not only on the second end surface (14b) but also on the first main surface (10a), the second main surface (10b), the first side surface (12a) and the second side surface (12b). You can wrap around part of it.
  • the first external electrode (8a) and the second external electrode (8b) are not in contact and are electrically separated.
  • the internal electrode layers (4) comprise a plurality of first internal electrode layers (4a) and a plurality of second internal electrode layers (4b).
  • Each of the first internal electrode layer (4a) and the second internal electrode layer (4b) has a substantially rectangular opposing electrode portion facing each other and external electrodes (8a, 8b) extending from the end faces (14a, 14b). ), and an extraction electrode portion connected to the That is, the plurality of first internal electrode layers (4a) extend to the first end surface (14a) via the extraction electrode portions and are electrically connected to the first external electrodes (8a) there.
  • a plurality of second internal electrode layers (4b) extend to the second end surface (14b) through lead electrode portions and are electrically connected to the second external electrodes (8b) there.
  • the first internal electrode layers (4a) and the second internal electrode layers (4b) are alternately laminated in the thickness direction T so as to face each other with the dielectric layer (2) interposed therebetween.
  • the first internal electrode layer (4a) and the second internal electrode layer (4b) facing each other across the dielectric layer (2) are not electrically connected. Therefore, when a voltage is applied via the external electrodes (8a, 8b) and the extraction electrode portion, the voltage between the counter electrode portion of the first internal electrode layer (4a) and the counter electrode portion of the second internal electrode layer (4b) charge is accumulated in Accumulated charges generate electrostatic capacitance, which functions as a capacitive element (capacitor).
  • the laminate (6) is composed of an inner layer (16), a first outer layer (18a), a second outer layer (18b), a first side (20a) and a second side (20b).
  • the first side (20a) is a layered region that extends along the first side (12a) and does not include the internal electrode layers (4a, 4b).
  • the second side portion (20b) is a layered region extending along the second side surface (12b) and not including the internal electrode layers (4a, 4b). That is, the first side portion (20a) is a region sandwiched between the end portions of the internal electrode layers (4a, 4b) on the side of the first side surface (12a) and the first side surface (12a). , a region sandwiched between the end portions of the internal electrode layers (4a, 4b) on the second side surface (12b) side and the second side surface (12b).
  • the first outer layer portion (18a) is sandwiched between the first side portion (20a) and the second side portion (20b) and is closest to the first main surface (10a) of the plurality of internal electrode layers (4a, 4b). It is a region sandwiched between the contacting internal electrode layers and the first main surface (10a).
  • the second outer layer portion (18b) is sandwiched between the first side portion (20a) and the second side portion (20b) and is closest to the second main surface (10b) of the plurality of internal electrode layers (4a, 4b). It is a region sandwiched between the contacting internal electrode layers and the second main surface (10b).
  • the inner layer portion (16) is a region sandwiched between the first outer layer portion (18a) and the second outer layer portion (18b), that is, the inner electrode layer closest to the first main surface (10a) and the second main surface (10b). It is a region arranged between the inner electrode layer closest to the .
  • This inner layer portion functions as a capacitive element.
  • the inner layer portion (16) that functions as a capacitive element is sandwiched between the first outer layer portion (18a) and the second outer layer portion (18b) in the lamination (thickness) direction. ) and the second side portion (20b) in the width direction.
  • the size of the multilayer ceramic capacitor (100) and the laminate (6) are not particularly limited.
  • the dimension L in the length direction is 0.2 mm or more and 3.2 mm or less
  • the dimension W in the width direction is 0.1 mm or more and 2.5 mm or less
  • the dimension T in the stacking direction is 0.1 mm or more and 2.5 mm or less. 1 to 3 show that the dimension L in the length direction is larger than the dimension W in the width direction, the multilayer ceramic capacitor of this embodiment is not limited to having such dimensions.
  • the L dimension in the length direction may be smaller than the W dimension in the width direction.
  • the dielectric layers constitute the inner layer portion of the multilayer ceramic capacitor together with the internal electrode layers.
  • the dielectric layer contains dielectric particles (dielectric grains).
  • the dielectric particles are composed of perovskite-type oxides and are the main component of the dielectric layer.
  • the dielectric layer consists of a sintered polycrystalline body (ceramic) in which a large number of dielectric grains are bonded via grain boundaries and triple points.
  • the dielectric layer can be said to be a dielectric ceramic whose main component is a perovskite oxide.
  • the main component is the component with the largest content in the dielectric layer.
  • the content of dielectric particles (perovskite-type oxide) as a main component in the dielectric layer may be 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more. It may be at least 90% by mass.
  • a perovskite-type oxide has a composition represented by the general formula: ABO 3 and has a cubic-like crystal structure such as cubic, tetragonal, orthorhombic, and rhombohedral at room temperature.
  • A-site element atoms hereinafter referred to as “A-site atoms”
  • B-site element atoms hereinafter referred to as “B-site atoms” are ionized to occupy the A-site and B-site of the perovskite structure, respectively.
  • A-site elements are exemplified by relatively large ion size elements such as barium (Ba), calcium (Ca), and strontium (Sr), and B-site elements are titanium (Ti), zirconium (Zr), and Elements with relatively small ion sizes such as hafnium (Hf) are exemplified.
  • the combination of A-site elements and B-site elements is not particularly limited as long as the perovskite structure is maintained.
  • Each of the A-site element and the B-site element may contain only one type of element, or may contain a combination of a plurality of elements.
  • the molar ratio of A-site elements to B-site elements may deviate from 1:1 as long as the perovskite structure is maintained.
  • perovskite-type oxides include barium titanate (BaTiO 3 )-based compounds, calcium titanate (CaTiO 3 )-based compounds, strontium titanate (SrTiO 3 )-based compounds, and mixed crystals and solid solutions thereof.
  • the A-site element comprises barium (Ba) and the B-site element comprises titanium (Ti).
  • the perovskite-type oxide is a barium titanate (BaTiO 3 )-based compound.
  • BaTiO3 has a large spontaneous polarization at room temperature. Therefore, it is a ferroelectric that exhibits a high dielectric constant.
  • the BaTiO 3 -based compound includes not only BaTiO3 but also BaTiO3 in which part of Ba is replaced with other A-site elements such as Sr and/or Ca, or part of Ti is replaced with Zr and/or Hf. substituted with other B-site elements.
  • the molar ratio of Ba in the A-site elements is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.
  • the ratio of Ti in the B-site elements is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more in terms of molar ratio.
  • the A-site element may contain no components other than Ba and the unavoidable impurity elements, and the B-site element may contain no components other than Ti and the unavoidable impurity elements.
  • the unavoidable impurities are components that are unavoidably mixed during the manufacturing process.
  • the dielectric layer may contain subcomponents. Secondary components include, but are not limited to, rare earth elements (RE), magnesium (Mg), manganese (Mn), iron (Fe), chromium (Cr), cobalt (Co), nickel (Ni), silicon (Si ), aluminum (Al), vanadium (V), and compounds thereof.
  • Rare earth elements (RE) are the group consisting of scandium (Sc) with atomic number 21, yttrium (Y) with atomic number 39, and lanthanum (La) with atomic number 57 to lutetium (Lu) with atomic number 71 in the periodic table.
  • RE Rare earth elements
  • lanthanum La
  • cerium Ce
  • Pr praseodymium
  • Nd neodymium
  • Sm samarium
  • Eu europium
  • Gd gadolinium
  • Tb terbium
  • Dy dysprosium
  • Ho holmium
  • Er erbium
  • Tm thulium
  • Yb lutetium
  • Lu yttrium
  • the form of existence of the subcomponents is not limited.
  • the subcomponent may be contained in any one of dielectric grains, grain boundaries, and triple points.
  • it When it is contained in the dielectric particles, it may be contained in a solid solution state. In that case, it may occupy the A site of the perovskite oxide (ABO 3 ), the B site, or both sites at the same time.
  • the distribution of the subcomponents in the dielectric particles may be uniform or non-uniform.
  • the dielectric particles may include core-shell particles.
  • Core-shell particles are those in which at least part of the subcomponents are solid-dissolved at a high concentration in the surface layer (shell portion) of the particle, and the subcomponents are solid-dissolved at a low concentration in the central portion (core portion) of the particle, or the subcomponents are solid. Particles with an undissolved structure (core-shell structure).
  • core-shell structure By giving the dielectric particles a core-shell structure, it is possible to flatten the temperature characteristics of the dielectric constant and improve the reliability. That is, since the core-shell particles have different subcomponent concentrations in the core portion and the shell portion, the dielectric constant temperature characteristics of the two are different. Therefore, it is possible to flatten the dielectric constant temperature characteristics of the entire particle.
  • subcomponents such as rare earth elements that act as donors and acceptors into the shell, it is possible to suppress the movement of oxygen vacancies that cause insulation deterioration and significantly improve the reliability of multilayer ceramic capacitors. Become.
  • Whether or not it has a core-shell structure is determined by measuring the concentration of the subcomponents at the center of the grain (core portion) for each subcomponent, the portion ( It can be judged by comparing with the accessory component concentration in the shell part). If the secondary component concentration in the shell portion is 150% or more of the concentration in the core portion, the particle can be determined to be a core-shell particle.
  • the dielectric particles may contain uniform solid solution particles.
  • Uniform solid-solution particles are particles in which subcomponents are uniformly solid-dissolved inside the particles, or particles in which subcomponents are not solid-dissolved.
  • Uniform solid solution particles are also called non-core-shell particles.
  • the core-shell particles have the advantage that the temperature characteristic of the dielectric constant can be flattened and the reliability can be improved, but there is a limit in increasing the dielectric constant itself. On the other hand, it is possible to remarkably increase the dielectric constant by using uniform solid-solution particles.
  • the dielectric layer at the center in the thickness direction of the inner layer portion contains particles having holes (particles with holes) as dielectric particles. (dielectric grain). That is, when the multilayer ceramic capacitor is processed to expose a plane (WT plane) that traverses the center in the length direction of the laminate and includes the width direction and the thickness direction, the dielectric layer at a predetermined position on the WT plane Some or all of the dielectric particles inside are particles with holes. In particles with holes, the holes are present inside the particles.
  • dielectric particles without voids may have low crystallinity. If the crystallinity of the particles is low, there is a risk that the auxiliary component elements will diffuse excessively into the particles during the firing process during the manufacture of the multilayer ceramic capacitor, degrading various properties. For example, when the purpose is to form core-shell particles, the subcomponent elements may diffuse through the shell into the core, destroying the core-shell structure. Further, when the purpose is to form uniform solid-solution system particles, it may become difficult to obtain the desired characteristics due to excessive solid-solution of the subcomponent elements in the particles.
  • the hole peripheral portions of the particles with holes have high crystallinity, excessive diffusion of subcomponent elements is suppressed.
  • the dielectric particles are core-shell particles, diffusion and solid solution of subcomponents do not proceed more than necessary even if grains are grown in the firing process. Since grain growth is possible without destroying the core-shell structure, it is possible to achieve both a high dielectric constant, flat temperature characteristics, and excellent reliability.
  • the number of holes in the particles with holes is not particularly limited.
  • a particle may contain a single vacancy in its interior, or may contain a plurality of vacancies.
  • the distribution of voids in the particles is not particularly limited. A void is typically present near the center of the particle.
  • the presence or absence of particles with holes and their ratio can be checked as follows.
  • the multilayer ceramic capacitor is processed by techniques such as polishing, grinding, and/or cutting to expose its cross section.
  • This cross section is a plane that traverses the central portion in the length (L) direction of the multilayer ceramic capacitor and includes the width (W) direction and the thickness (T) direction, that is, the WT plane.
  • the obtained cross section is observed with a transmission electron microscope (TEM) to obtain a high-angle annular dark field (HAADF) image, and based on this image, the presence or absence of particles with holes and their ratio are examined.
  • the vacancies can be easily spotted as they appear as black dots in the particles.
  • Observation is performed on the substantially central portion of the WT plane in the thickness (T) direction. If a dielectric layer exists in the central portion in the thickness direction, the dielectric layer may be observed. On the other hand, when an internal electrode layer exists in the central portion in the thickness direction, the dielectric layer adjacent to the internal electrode layer may be observed. Observation is performed for 100 or more dielectric particles. For example, observation is performed with a field of view of 1000 nm ⁇ 1000 nm, and the number of particles with holes is counted for the dielectric particles present in this field of view. If there are not more than 100 dielectric particles in this field of view, then a plurality of adjacent fields of view should be examined.
  • observation may be performed in a total visual field area of 3 ⁇ m ⁇ 3 ⁇ m by connecting a plurality of visual fields. Then, the number (N) of the dielectric particles and the number (n) of the particles with holes are counted, and the number ratio (n/N) of the particles with holes is obtained from these.
  • the particles with holes are present near the center in the width direction of the inner layer. That is, in a cross section across the central portion in the length direction of the laminate, the dielectric layer at the center in the thickness direction of the inner layer intermediate region preferably contains particles with holes as the dielectric particles.
  • the inner layer intermediate region is a region located in the middle of the inner layer portion in the width direction. Specifically, when the laminate is divided into the first inner layer side region, the second inner layer side region, and the inner layer intermediate region, the region sandwiched between the first inner layer side region and the second inner layer side region is This is the inner layer intermediate region.
  • the first inner layer side region is a region within the inner layer portion that occupies a portion equal to or less than the end distance from the interface between the inner layer portion and the first side portion.
  • the edge distance is the smaller one of W/10 and 40 ⁇ m, where W is the width of the laminate.
  • the first inner layer side region can also be said to be a region within the inner layer portion sandwiched between the interface between the inner layer portion and the first side portion and a surface separated from the interface by the edge distance.
  • the second inner layer side region is a region within the inner layer portion that occupies a portion that is equal to or less than the end distance from the interface between the inner layer portion and the second side portion.
  • the second inner layer side region can also be said to be a region within the inner layer sandwiched between the interface between the inner layer and the second side and a surface separated from the interface by the edge distance.
  • the number ratio (Cn/CN) of particles with holes in the dielectric particles in the center in the thickness direction of the inner layer intermediate region is 15% or more. is desirable.
  • the number ratio (Cn/CN) may be 20% or more, 25% or more, 30% or more, 35% or more, or 40% or more.
  • the upper limit of the number ratio (Cn/CN) is not particularly limited. It may be 100% or less, 80% or less, or 60% or less.
  • the particles with holes are present near the widthwise end of the inner layer. That is, in a cross section across the central portion in the length direction of the laminate, the dielectric layer at the center in the thickness direction of at least one of the first inner layer side region and the second inner layer side region is composed of dielectric particles with holes. should be included as This makes it possible to further improve the reliability.
  • the electric field is concentrated near the ends of the internal electrode layers, so dielectric breakdown is likely to occur near the ends.
  • By providing particles with highly crystalline voids in the dielectric layer near the edge it is possible to suppress the progression of dielectric breakdown, and as a result, it is possible to remarkably improve the reliability.
  • the number ratio ( Wn/WN) is desirably larger than the number ratio (Cn/CN) of particles with holes in the dielectric particles at the center of the inner layer intermediate region in the thickness direction.
  • the number ratio of particles with holes in the dielectric particles in the center in the thickness direction of at least one of the first inner layer side region and the second inner layer side region (Wn /WN) is preferably 25% or more.
  • the average pore diameter of the pores is preferably 1 nm or more and 50 nm or less, particularly preferably 10 nm or more and 30 nm or less.
  • the average particle size of the dielectric particles is preferably 100 nm or more and 500 nm or less, particularly preferably 130 nm or more and 300 nm or less.
  • the average particle diameter mentioned above is the average particle diameter of all dielectric particles including not only particles with holes but also particles without holes.
  • the thickness of the dielectric layer is preferably 0.30 ⁇ m or more and 1.00 ⁇ m or less, more preferably 0.40 ⁇ m or more and 0.50 ⁇ m or less, and even more preferably 0.40 ⁇ m or more and 0.45 ⁇ m or less.
  • the number of dielectric layers is not particularly limited. Preferably, the number of dielectric layers forming the outer layer portion and the inner layer portion is 100 or more and 2000 or less.
  • the composition of the dielectric layer occupying the inner layer portion is not particularly limited.
  • a suitable composition contains barium titanate (BaTiO 3 ) as a main component, and further contains 0.6 to 2.0 mol parts of dysprosium (Dy) and manganese ( Mn) 0.08 to 0.4 mol parts, magnesium (Mg) 0.01 to 0.2 mol parts, silicon (Si) 0.6 to 2.0 mol parts, nickel (Ni) 0.2 to 5 .0 mol part, 0.04 to 0.3 mol part of aluminum (Al), and 0.04 to 0.2 mol part of vanadium (V).
  • the internal electrode layers (first internal electrode layer, second internal electrode layer) form an internal layer portion together with the dielectric layer.
  • the internal electrode layer is composed of a counter electrode portion and a lead electrode portion, and the counter electrode portion sandwiches a dielectric layer to function as a capacitor.
  • the extraction electrode section has a function of electrically connecting the counter electrode section and the external electrode.
  • the internal electrode layers contain a conductive metal.
  • Known electrode materials such as nickel (Ni), copper (Cu), silver (Ag), palladium (Pd), silver (Ag)-palladium (Pd) alloy and/or gold (Au) are used as the conductive metal. Just do it.
  • base metals such as Ni and Cu are preferable, and Ni is particularly preferable.
  • the internal electrode layers may contain components other than the conductive metal.
  • Other components may include ceramic components that act as co-materials.
  • ceramic components By adding the common material, it is possible to match the shrinkage behavior of the internal electrode layers with that of the dielectric layers in the firing process of manufacturing the multilayer ceramic capacitor. Therefore, it is possible to suppress the occurrence of defects such as peeling of the internal electrode layers due to the difference in contraction behavior.
  • dielectric particles such as BaTiO 3 based compound contained in the dielectric layer are suitable.
  • the thickness of the internal electrode layer is preferably 0.30 ⁇ m or more and 0.40 ⁇ m or less, more preferably 0.30 ⁇ m or more and 0.35 ⁇ m or less.
  • the internal electrode thickness By setting the internal electrode thickness to a predetermined value or more, it is possible to prevent problems such as electrode breakage from occurring. Further, by setting the thickness to a predetermined value or less, it is possible to prevent a decrease in the ratio of the dielectric layer in the capacitor, which contributes to an increase in capacity. Further, the number of internal electrode layers is preferably 10 or more and 1000 or less.
  • Tin (Sn) may exist at the interface between the dielectric layer and the internal electrode layer.
  • Sn When Sn is present, Sn may be present in a layered form parallel to the internal electrode layers, or may be scattered. Further, Sn may be solid-solubilized inside the internal electrode layers, or may be solid-solubilized in the dielectric particles constituting the dielectric layers.
  • the outer layer portions are provided above and below the inner layer portion.
  • the outer layer portion is a region that is made of dielectric ceramic and does not include internal electrode layers therein.
  • the composition of the outer layer portion may be the same as or different from the dielectric layer contained in the inner layer portion.
  • the dielectric green sheet used for forming the inner layer may also be used for forming the outer layer when manufacturing the multilayer ceramic capacitor.
  • the side portions are provided along side surfaces of the multilayer ceramic capacitor so as to sandwich the inner layer portion and the outer layer portion.
  • the inner layer side portion is also called a side gap.
  • the side portion (side gap portion) is a region that is made of dielectric ceramic and does not include internal electrode layers therein. By providing the side portion, it is possible to prevent moisture from entering the inner layer portion from the side surface.
  • the side portion may be formed integrally with the inner layer portion and the outer layer portion when manufacturing the multilayer ceramic capacitor.
  • the dielectric layers forming the side portions are continuous in composition and microstructure with the dielectric layers forming the inner layer portion and/or the outer layer portion.
  • the side portions may be formed separately from the inner and outer layer portions.
  • the side green bodies are attached to the side surfaces of the laminated chip that will be the inner layer and the outer layer to form the green body, and the green body is fired.
  • the dielectric layers forming the side portions are not continuous in composition and/or microstructure with the dielectric layers forming the inner layer portion and/or the outer layer portion. There is therefore a physical and chemical boundary between the sides and the inner and/or outer layer.
  • the first side and the second side contain dielectric particles containing barium (Ba) and titanium (Ti), and more than 1.00 mol parts per 100 mol parts of titanium (Ti)3.
  • Mg amount to 1.00 mol parts or more or the Mn amount to 0.50 mol parts or more, it is possible to further improve the moisture resistance load characteristics. Further, by setting the Mg amount to 3.00 mol parts or less and the Mn amount to 2.00 mol parts or less, it is possible to suppress the decrease in capacity.
  • the external electrodes serve as input/output terminals of the multilayer ceramic capacitor.
  • a known configuration can be adopted as the external electrode.
  • a base electrode layer and a plated layer disposed on the base electrode layer may be provided.
  • the underlying electrode layer comprises at least one layer selected from layers such as a baking layer, a resin layer, and a thin film layer.
  • the baked layer is formed by applying a conductive paste containing glass and metal to the laminate and baking the paste. Baking may be performed at the same time as firing the laminate, or may be performed after firing the laminate.
  • the stoving layer may be a single layer or may be composed of multiple layers.
  • the metals contained in the baking layer are preferably copper (Cu), nickel (Ni), silver (Ag), palladium (Pd), silver (Ag)-palladium (Pd) alloys, and/or gold (Au).
  • the resin layer contains conductive particles and a thermosetting resin.
  • the resin layer may be a single layer, or may be composed of multiple layers.
  • the thin film layer is a layer having a thickness of 1 ⁇ m or less, which is formed by a thin film forming method such as a sputtering method and a vapor deposition method, and in which metal particles are deposited.
  • the plating layer is a metal such as copper (Cu), nickel (Ni), tin (Sn), silver (Ag), palladium (Pd), silver (Ag)-palladium (Pd), and/or gold (Au).
  • the plating layer may be a single layer or may be composed of multiple layers.
  • a suitable plating layer has a two-layer structure of Ni plating and Sn plating.
  • the Ni plating layer can prevent erosion of the underlying layer by solder when mounting the multilayer ceramic capacitor.
  • the Sn plating layer has the effect of facilitating the mounting of the multilayer ceramic capacitor because it enhances the wettability of the solder.
  • the external electrode layer may be composed of the plating layer without providing the base electrode layer.
  • the plating layer is provided directly on the laminate and directly connected to the lead electrode portion of the internal electrode layer.
  • a catalyst may be provided on the laminate.
  • the plating layer includes a first plating layer and a second plating layer provided on the first plating layer. Further, another plating layer may be provided on the second plating layer.
  • the first plating layer and the second plating layer are, for example, copper (Cu), nickel (Ni), tin (Sn), lead (Pd), gold (Au), silver (Ag), palladium (Pd), bismuth ( Bi), and one metal selected from the group consisting of zinc (Zn), or an alloy containing the metal.
  • the first plating layer preferably contains Cu, which has good bonding properties with Ni.
  • the first plating layer preferably contains Ni, which has good solder barrier performance.
  • the second plating layer preferably contains Sn or Au, which have good solder wettability.
  • the plating layer is not limited to the first plating layer and the second plating layer.
  • the plating layer may be composed only of the first plating layer without providing the second plating layer.
  • Another plating layer may be provided on the second plating layer.
  • the plated layer preferably does not contain glass.
  • it is preferable that the metal ratio of the plating layer is 99% by volume or more.
  • the plated layer has grain growth along the thickness direction and has a columnar shape.
  • a manufacturing method of the multilayer ceramic capacitor of the present embodiment is not limited as long as it satisfies the requirements described above. However, it is preferably manufactured by the following method.
  • a preferred manufacturing method includes the following steps: a step of synthesizing a main component raw material for a dielectric layer (synthesis step); A step of adding and mixing a binder and a solvent to the raw material to form a slurry, forming a dielectric green sheet from the obtained slurry (forming step), using a conductive paste for internal electrodes, A step of printing a patterned conductive paste layer (printing step), a step of laminating and press-bonding a plurality of dielectric green sheets to produce a laminated block (lamination step), and cutting the obtained laminated block.
  • a step of forming laminated chips (cutting step), a step of attaching side green bodies to the side surfaces of the obtained laminated chips to form green body portions (side forming step), and removing the obtained green body portions. It comprises a step of applying a binder treatment and a firing treatment to form an element body (firing step), and a step of forming external electrodes on the obtained element body to form a multilayer ceramic capacitor (external electrode forming step). Details of each step are described below.
  • ⁇ Synthesis process> main component raw materials used for forming the dielectric layer are synthesized.
  • the raw material for the main component is synthesized by a liquid phase method such as a sol-gel method, an alkoxide method, a solvothermal method, or a hydrothermal synthesis method.
  • sol-gel method sol or gel of inorganic or organic salts of Ba and Ti are used as raw materials, which are mixed and fired to produce oxide powder.
  • alkoxides of Ba and Ti are used as raw materials, which are mixed and fired to produce oxide powder.
  • solvothermal method inorganic or organic compounds of Ba and Ti are placed in a sealed container together with a solvent, and high temperature and high pressure are applied to synthesize oxide powder.
  • the hydrothermal method is a kind of solvothermal method and uses water as a solvent.
  • ⁇ Mixing process> In the mixing step, subcomponent (Ni, Re, Mg, Mn, Si, Al, V, etc.) materials are mixed with the main component material to form a dielectric material.
  • Known ceramic raw materials such as oxides, carbonates, hydroxides, nitrates, organic acid salts, alkoxides and/or chelate compounds may be used as auxiliary component raw materials.
  • a mixing method is not particularly limited. For example, there is a method of wet-mixing and pulverizing the weighed main component raw materials and sub-component raw materials together with pulverizing media and pure water using a ball mill. If wet mixing is used, the mixture may be dried.
  • a binder and a solvent are added to and mixed with the dielectric raw material to form a slurry, and the obtained slurry is formed into a dielectric green sheet. After firing, the dielectric green sheets become dielectric layers constituting the inner and outer layers of the multilayer ceramic capacitor.
  • a binder a known organic binder such as a polyvinyl butyral binder may be used.
  • a solvent a known organic solvent such as toluene or ethanol may be used. Additives such as plasticizers may be added as necessary.
  • the molding may be performed by a known method such as a lip method. The sheet thickness after molding is, for example, 1 ⁇ m or less.
  • a conductive paste is used to form a patterned conductive paste layer on the surface of the dielectric green sheet.
  • the conductive paste layers become internal electrode layers after firing.
  • a conductive material such as nickel (Ni), copper (Cu), silver (Ag), palladium (Pd), or an alloy containing these may be used as the conductive metal contained in the conductive paste.
  • nickel (Ni) is preferred.
  • a ceramic component that acts as a common material may also be added to the conductive paste.
  • the raw material of the main component of the dielectric layer can be used.
  • a method of forming the conductive paste layer is not particularly limited. For example, methods such as screen printing and gravure printing can be used.
  • ⁇ Lamination process> In the lamination step, a plurality of dielectric green sheets are laminated and pressure-bonded to produce a laminated block. At this time, a plurality of dielectric green sheets having conductive paste layers formed thereon are laminated so as to be sandwiched from above and below by dielectric green sheets having no conductive paste layers formed thereon. The green sheet without the conductive paste layer formed thereon becomes the outer layer of the multilayer ceramic capacitor through a sintering process. On the other hand, the green sheet on which the conductive paste layer is formed becomes the dielectric layer constituting the inner layer of the multilayer ceramic capacitor. The number of laminated green sheets may be adjusted so as to obtain the required capacity.
  • the obtained laminated block is cut into laminated chips. Cutting may be performed so that chips of a predetermined size are obtained and at least a portion of the conductive paste layer is exposed on the end face of the laminated chip.
  • a side forming step is provided as required.
  • the side portions are formed separately from the inner layer portion and the outer layer portion.
  • the side green body is attached to the side surface of the laminated chip to form the green body.
  • the side green body covers the conductive paste layer exposed on the side surface of the laminated chip.
  • the side green bodies become the sides of the multilayer ceramic capacitor after firing.
  • the raw material for the side green body the main component raw material and sub-component raw material used for the dielectric layer fabrication can be used.
  • the composition of the side portions need not be the same as the composition of the dielectric layer, and may be different. For example, only some of the subcomponents of the dielectric layer may be used, or subcomponents different from the dielectric layer may be added.
  • the composition of the sides may be the same as that of the dielectric layer.
  • the preparation and attachment of the side green body may be performed by a known method.
  • a technique of forming a green sheet from the raw material powder for the side portion and bonding the green sheet to the side surface of the laminated chip in order to ensure the adhesion of the green sheets, an adhesion aid such as an organic solvent may be applied in advance to the side surfaces of the laminated chips.
  • an adhesion aid such as an organic solvent may be applied in advance to the side surfaces of the laminated chips.
  • a method of preparing a paste from the raw material powder for the side portion, applying the paste to the side surface of the laminated chip, and drying the paste can be used.
  • the side green body may be a single layer, or may be a laminate comprising a plurality of layers.
  • a side green body composed of a laminate can be obtained by a technique of laminating a plurality of green sheets on the side surface of a laminated chip or a technique of repeating application and drying of paste.
  • the side portions are formed integrally with the inner layer portion and the outer layer portion, part of the dielectric green sheets laminated in the lamination step becomes the side portions. No need to set.
  • barrel polishing is applied to the laminated chip or green body. This treatment makes it possible to round the corners and/or ridges of the laminated chip or green body.
  • the firing step the laminated chip or the green body portion is subjected to binder removal treatment and firing treatment to form the body portion.
  • the conductive paste layers and dielectric green sheets are co-sintered by the firing process to form internal electrode layers and dielectric layers, respectively.
  • the conditions for the binder removal treatment may be determined according to the type of organic binder contained in the green sheet and the conductive paste layer.
  • the firing treatment may be performed at a temperature at which the laminated chip is sufficiently densified. For example, the temperature may be kept at 1200° C. or more and 1300° C. or less for 0 minute or more and 10 minutes or less.
  • the firing is performed in an atmosphere in which the BaTiO 3 -based compound, which is the main component, is not reduced and oxidation of the conductive material is suppressed.
  • it may be carried out in an N 2 —H 2 —H 2 O airflow with an oxygen partial pressure of 1.8 ⁇ 10 ⁇ 9 to 8.7 ⁇ 10 ⁇ 10 MPa. Further, annealing may be performed after firing.
  • external electrodes are formed on the element body to form a multilayer ceramic capacitor. Formation of the external electrodes may be performed by a known method. For example, a base layer is formed by coating and baking a conductive paste containing a conductive component such as Cu or Ni as a main component on the exposed end face of the element body where the internal electrodes are pulled out.
  • the underlayer may be formed by applying a conductive paste to both end surfaces of the green body portion before firing, and then performing a firing treatment. After forming the underlayer, electrolytic plating may be applied to form a plating film of Ni, Sn, or the like on the surface of the underlayer. A laminated ceramic capacitor is thus produced.
  • the barium titanate powder was produced by a so-called hydrothermal synthesis method. First, titanium oxide (TiO 2 ) powder and barium hydroxide (Ba(OH) 2 ) powder were weighed, and pure water was added to prepare a slurry. Then, the prepared slurry was placed in a sealed container, and the temperature of the slurry was raised to 200 to 250° C. while stirring. Then, the mixture was held at 200 to 250° C. for 4 to 24 hours to advance the liquid phase reaction. After that, the pressure inside the sealed container was returned to the atmospheric pressure, the heating of the sealed container was stopped, and the slurry was allowed to stand. After cooling, the slurry was removed from the sealed container and placed in a dryer to evaporate water. The barium titanate powder thus obtained was used as a raw material for the main component.
  • TiO 2 titanium oxide
  • Ba(OH) 2 barium hydroxide
  • Ni, Re, Mg, Mn, Si, Al, V Subcomponent (Ni, Re, Mg, Mn, Si, Al, V) materials were weighed separately from the main component materials.
  • auxiliary component raw materials nickel oxide (NiO) , rare earth oxides ( Dy2O3 , etc.), magnesium carbonate ( MgCO3 ), manganese carbonate ( MnCO3 ), silicon oxide ( SiO2 ), aluminum oxide ( Al2O3 ), and vanadium oxide (V 2 O 5 ).
  • the subcomponent raw materials were added to the main component raw materials, wet-mixed using a ball mill, dried and heat-treated to obtain a dielectric raw material.
  • a polyvinyl butyral-based binder and ethanol as an organic solvent were added to the obtained dielectric raw material, and wet-mixed by a ball mill for a predetermined time to prepare a slurry. This slurry was formed into a sheet to produce a dielectric green sheet.
  • a conductive paste mainly composed of Ni was screen-printed on the surface of the obtained dielectric green sheet to form a pattern of conductive paste layers that would become internal electrode layers.
  • a plurality of green sheets each having a conductive paste layer formed thereon were laminated, and green sheets without a conductive paste layer formed thereon were placed above and below the green sheets, and the whole was pressed together to produce a laminated block.
  • the obtained laminated block was cut with a dicing saw into laminated chips. Lamination was performed so that the ends from which the conductive paste layers were drawn out were alternated. Also, the cutting was performed so that the conductive paste layer was exposed on the side surface.
  • a side green sheet (side green body) was attached to both sides of the cut laminated chip where the conductive paste layer was exposed to form a green element body.
  • the side green sheets were produced in the same manner as the dielectric green sheets, except that the blending amounts of the main component raw material and subcomponent raw material were changed.
  • the obtained green body portion was heat-treated in an N 2 stream at a maximum temperature of 270° C., and further heat-treated in an N 2 —H 2 O—H 2 stream at a maximum temperature of 800° C. After that, it was calcined in a N 2 —H 2 O—H 2 stream.
  • the firing was performed under the conditions of a maximum temperature of 1050 to 1090° C., a temperature increase rate of 50° C./min, a keeping time of 60 minutes, and an oxygen partial pressure of 7.8 ⁇ 10 ⁇ 11 to 3.3 ⁇ 10 ⁇ 9 MPa. rice field.
  • the maximum temperature was 1230 to 1400° C.
  • the temperature increase rate was 20 to 60/sec
  • the keep time was shorter than in the comparative example
  • the oxygen partial pressure was 5.0 ⁇ 10 ⁇ 13 to 1.7 ⁇ 10 ⁇ 12.
  • Firing was performed under the condition of MPa. Subsequently, heat treatment was performed for 60 minutes at a maximum temperature of 1050° C. in an N 2 —H 2 O—H 2 stream. Thus, a multilayer ceramic capacitor laminate was obtained.
  • a conductive paste containing copper (Cu) as a main component was applied to the end faces of the laminate obtained by firing where the internal electrode layers were drawn out. After that, the applied conductive paste was baked at 900° C. to form a base layer for the external electrodes. Further, Ni plating and Sn plating were performed in this order on the surface layer of the underlayer by wet plating. Thus, a laminated ceramic capacitor was produced.
  • Cu copper
  • the manufactured laminated ceramic capacitor had a length L dimension of 1.0 mm, a width direction W dimension of 0.5 mm, and a thickness direction T dimension of 0.5 mm.
  • the thickness of the dielectric layer in the inner layer portion was 0.48 ⁇ m
  • the thickness of the internal electrode layer was 0.38 ⁇ m
  • the number of dielectric layers was 50 layers.
  • an SEM image of the dielectric particles in the dielectric layer in the exposed cross section was taken under conditions of a magnification of 5000 times, an acceleration voltage of 15 kV, and a field of view of 30 ⁇ m ⁇ 30 ⁇ m. Then, using image processing software, the edges of all the dielectric particles were recognized, the cross-sectional areas of the particles were calculated, and the equivalent circle diameter was calculated as the diameter of the particles from this area. The diameters of all the dielectric particles included in the imaged range were measured, and the average value was obtained, except for the dielectric particles that were missing and imaged.
  • TEM observation> Using a transmission electron microscope (TEM), the WT surface of the multilayer ceramic capacitor was observed to examine the presence or absence of particles with holes and their ratio. Specifically, the laminated ceramic capacitor was polished to the center in the length (L) direction to expose the WT surface, and further processed to obtain a thin piece sample including the WT surface. Then, a thin section sample was observed using a TEM, and a high-angle annular dark field (HAADF) image was obtained. During the observation, the cross section (WT surface) of the multilayer ceramic capacitor was divided into a side portion, an outer layer portion, and an inner layer portion, and the inner layer portion was further divided into an inner layer intermediate region and an inner layer side region.
  • TEM transmission electron microscope
  • Observation was then performed with a field of view of 1000 nm ⁇ 1000 nm in the center of each of the inner layer intermediate region and the inner layer side region. Observations were made on 100 or more dielectric particles. When one field of view did not contain 100 or more dielectric particles, a plurality of fields of view were connected for observation.
  • the number of dielectric particles (CN, WN) and the number of particles with holes (Cn, Wn) in the dielectric particles were counted, and the number of particles with holes Ratios (Cn/CN, Wn/WN) were calculated.
  • the pore diameters of a plurality of particles with holes were measured, and the average value was calculated.
  • ⁇ Dielectric constant> The capacitance of the dielectric layer was measured using an automatic bridge type measuring machine. The measurement was performed on 100 samples under the conditions of a temperature of 25° C., an effective voltage of 0.5 Vrms, and a frequency of 1 kHz. From the obtained capacitance, the dielectric constant ( ⁇ r ) was calculated using the thickness of the dielectric layer and the area of the counter electrode, and the average value was obtained. Based on the relative permittivity values obtained, the samples were graded according to the following criteria.
  • A Dielectric constant of 3000 or more and 4800 or less
  • B Dielectric constant of 2500 or more and less than 3000, or more than 4800 and 5000 or less
  • C Dielectric constant of less than 2500 or more than 5000
  • ⁇ Capacity temperature coefficient> For five samples, the capacitance was measured within a temperature range of -55°C to 105°C under the conditions of an effective voltage of 1 Vrms and a frequency of 1 kHz, and the temperature coefficient of capacitance (change rate) was calculated. Based on the obtained temperature coefficient values, the samples were graded according to the following criteria.
  • Table 1 summarizes the evaluation results of the multilayer ceramic capacitors obtained in Comparative Examples 1 to 3 and Examples 1 to 20.
  • the samples of Examples 1 to 20 in which particles with holes were included in the dielectric layer of the inner layer had a high relative permittivity ( ⁇ r ) and flattened capacity-temperature characteristics, resulting in reliability. improved durability (high temperature load life).
  • ⁇ r relative permittivity
  • the greater the number ratio of the particles with holes the more remarkable the effect obtained.
  • the ratio of the number of particles with holes in the inner layer intermediate region is 15% or more
  • the number ratio of the particles with holes in the inner layer side region is 25% or more
  • the average pore diameter of the particles with holes is 10 nm or more and 30 nm or less.

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