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WO2025248979A1 - Condensateur céramique multicouche - Google Patents

Condensateur céramique multicouche

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Publication number
WO2025248979A1
WO2025248979A1 PCT/JP2025/014130 JP2025014130W WO2025248979A1 WO 2025248979 A1 WO2025248979 A1 WO 2025248979A1 JP 2025014130 W JP2025014130 W JP 2025014130W WO 2025248979 A1 WO2025248979 A1 WO 2025248979A1
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WIPO (PCT)
Prior art keywords
internal electrode
region
dielectric layer
multilayer ceramic
ceramic capacitor
Prior art date
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Pending
Application number
PCT/JP2025/014130
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English (en)
Japanese (ja)
Inventor
徹 若松
将司 吉田
雅之 石原
義人 齊藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Filing date
Publication date
Application filed by Murata Manufacturing Co Ltd filed Critical Murata Manufacturing Co Ltd
Publication of WO2025248979A1 publication Critical patent/WO2025248979A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Definitions

  • This disclosure relates to multilayer ceramic capacitors.
  • Patent Document 1 JP 2022-143403 A discloses a multilayer ceramic capacitor with improved reliability achieved by the presence of an interfacial layer composed of a non-perovskite oxide containing tin in the area of contact with the internal electrode layer inside a dielectric layer primarily composed of a perovskite oxide containing barium and titanium.
  • the dielectric layers are often constructed from perovskite oxides containing barium and titanium in order to achieve a high dielectric constant.
  • an interfacial layer composed of a non-perovskite oxide containing tin is formed at the location where the dielectric layer contacts the internal electrode layer, which tends to reduce the proportion of the area composed of perovskite oxide in the dielectric layer.
  • the present disclosure aims to provide a multilayer ceramic capacitor in which the proportion of the area in the dielectric layer that is composed of a perovskite structure (e.g., the proportion of layers that have a perovskite structure per unit thickness) is prevented from decreasing, even when the area of the dielectric layer that is in contact with the internal electrode layer contains tin.
  • a perovskite structure e.g., the proportion of layers that have a perovskite structure per unit thickness
  • a multilayer ceramic capacitor according to the present disclosure includes a ceramic element body in which multiple dielectric layers and multiple internal electrode layers are alternately stacked.
  • the dielectric layers contain ceramic as a primary component.
  • the ceramic contains barium and titanium.
  • the dielectric layers further contain tin.
  • the internal electrode layers contain nickel as a primary component.
  • the internal electrode layers have a first region in which tin is dissolved, at least near the interface with the dielectric layer.
  • the dielectric layers have a second region in which a perovskite structure containing barium and titanium is formed. The second region is in contact with the internal electrode layers.
  • the perovskite structure in the second region contains tin as a solid solution.
  • This disclosure makes it possible to provide a multilayer ceramic capacitor in which the reduction in the proportion of the area in the dielectric layer that is composed of a perovskite structure is suppressed, even when the area of the dielectric layer that is in contact with the internal electrode layer contains tin.
  • FIG. 1 is a cross-sectional view showing an example of a multilayer ceramic capacitor, which is one embodiment of a multilayer electronic component according to the present disclosure.
  • 3 is a schematic view of a transmission electron microscope image of a region including an interface between a dielectric layer and an internal electrode layer in a cross section of the ceramic body in the stacking direction.
  • FIG. 1 is a transmission electron microscope image of a multilayer ceramic capacitor produced in an example.
  • 1 is a transmission electron microscope image of a multilayer ceramic capacitor produced in an example.
  • ⁇ Multilayer ceramic capacitors> 1 is a cross-sectional view of a multilayer ceramic capacitor 100.
  • the multilayer ceramic capacitor 100 includes a ceramic body 10.
  • the ceramic body 10 is formed by alternately stacking a plurality of dielectric layers 11 and a plurality of internal electrode layers 12.
  • the ceramic body 10 has a first main surface and a second main surface that face each other in the stacking direction, a first side surface and a second side surface that face each other in the width direction perpendicular to the stacking direction, and a first end face 13a and a second end face 13b that face each other in the length direction perpendicular to the stacking direction and the width direction.
  • the multiple dielectric layers 11 have outer layer portions and inner layer portions.
  • the outer layer portions are arranged between the first main surface of the ceramic body 10 and the internal electrode layer 12 closest to the first main surface, and between the second main surface and the internal electrode layer 12 closest to the second main surface.
  • the inner layer portions are arranged in the area sandwiched between these two outer layer portions.
  • the number of dielectric layers 11 in the multilayer ceramic capacitor 100 is, for example, 100 to 900.
  • Dielectric layer 11 contains ceramic as its main component.
  • the main component refers to the component that has the largest content by mass among the constituent components.
  • the ceramic content in dielectric layer 11 may be 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, or 99% by mass or more based on the total mass of dielectric layer 11.
  • the ceramic may contain a perovskite-type oxide (hereinafter also referred to as perovskite oxide) containing titanium (Ti) and barium (Ba) as a main component.
  • the ceramic may have crystalline particles composed of the perovskite oxide.
  • the perovskite oxide may be a barium titanate ( BaTiO3 )-based compound.
  • BaTiO3 is a perovskite-type oxide represented by the general formula: ABO3 .
  • BaTiO3 exhibits a tetragonal crystal structure at room temperature and is a ferroelectric material exhibiting a high dielectric constant.
  • the dielectric constant of the dielectric ceramic can be increased, enabling the capacitor to have a large capacitance.
  • the content of the perovskite oxide in the ceramic may be, for example, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more.
  • the ceramic may have a grain structure as described below.
  • the BaTiO3 - based compound is not particularly limited as long as it is a perovskite-type oxide primarily containing Ba and Ti.
  • the BaTiO3 -based compound may be BaTiO3 , or may be BaTiO3 in which part of the Ba and/or Ti contained in BaTiO3 is substituted with other elements.
  • part of the Ba may be substituted with strontium (Sr) and/or calcium (Ca)
  • part of the Ti may be substituted with zirconium (Zr) and/or hafnium (Hf).
  • the dielectric layer 11 further contains tin (Sn).
  • Sn tin
  • the areas of the dielectric layer in contact with the internal electrode layers tend to contain tin, which tends to increase the reliability of the multilayer ceramic capacitor.
  • the Sn may be dispersed throughout the dielectric layer 11.
  • the Sn may be dissolved in either the A element site (e.g., the Ba site) or the B element site (e.g., the Ti site) of the perovskite structure containing Ba and Ti present in the dielectric layer 11, or may be dissolved in both.
  • the Sn may be dissolved in more B element sites than in A element sites.
  • the thickness of the dielectric layer 11 may be, for example, 0.4 ⁇ m or less.
  • the thickness of the dielectric layer 11 is preferably 0.1 ⁇ m or more.
  • the thickness of the dielectric layer 11 is the thickness of a single dielectric layer in the internal layer portion (the dielectric layer existing between two opposing internal electrode layers).
  • the thickness of the dielectric layer 11 can be measured, for example, in a scanning electron microscope (hereinafter sometimes abbreviated as SEM) or transmission electron microscope (hereinafter sometimes abbreviated as TEM) image of a cross section of the ceramic body 10 in the stacking direction.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the internal electrode layer 12 contains nickel (Ni) as its main component.
  • Ni nickel
  • the Ni content in the internal electrode layer 12 may be, for example, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more.
  • the internal electrode layers 12 contain Sn.
  • the Sn contained in the internal electrode layers 12 may be present in a solid solution state in the first region described below, where Sn contained in the dielectric layers (pre-sintered dielectric sheets) migrates to the internal electrode layers during the sintering process of the ceramic body described below.
  • the internal electrode layers 12 may contain at least one other conductive metal selected from the group consisting of copper (Cu), silver (Ag), palladium (Pd), and alloys containing these.
  • the internal electrode layers 12 may further contain other components. Examples of other components include ceramic components that function as co-materials. An example of the ceramic component is a BaTiO3 -based compound contained in the dielectric layers 11.
  • the thickness of the internal electrode layers 12 may be, for example, 0.4 ⁇ m or less. When the thickness of the internal electrode layers 12 is 0.4 ⁇ m or less, the decrease in the proportion of the dielectric layers 11 in the multilayer ceramic capacitor 100 is suppressed, and as a result, the decrease in capacitance tends to be more easily suppressed.
  • the thickness of the internal electrode layers 12 may be, for example, 0.3 ⁇ m or more. When the thickness of the internal electrode layers 12 is 0.3 ⁇ m or more, defects such as electrode discontinuities tend to be more easily suppressed.
  • the thickness of the internal electrode layers 12 can be measured in an SEM or TEM image of a cross section in the stacking direction of the ceramic body 10.
  • the internal electrode layer 12 has a first region in which Sn is dissolved, at least near the interface with the dielectric layer 11.
  • the presence of the first region near the interface with the dielectric layer 11 in the internal electrode layer 12 can be confirmed, for example, by combining TEM observation and EDX analysis of a region including the interface between the dielectric layer 11 and the internal electrode layer 12 in a cross section of the ceramic body 10 in the stacking direction.
  • TEM observation can be, for example, high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM).
  • HAADF-STEM is a technique in which a focused electron probe is scanned on a sample, and high-angle scattered transmitted electrons that pass through the sample are detected with an annular detector for two-dimensional mapping.
  • HAADF-STEM produces images with atomic resolution, and image interpretation is easy because there is no image contrast inversion.
  • the presence of the first region can be confirmed by confirming the atomic positions in the image using HAADF-STEM observation and identifying the atoms using EDX.
  • the internal electrode layer 12 may have Sn in a solid solution in the central region.
  • the central region is an area inside the internal electrode layer 12 that exists outside the first region.
  • the concentration of Sn in the first region is higher than the concentration of Sn in the central region.
  • the dielectric layer 11 has a second region in which a perovskite structure containing Ba and Ti is formed.
  • the second region is a region in contact with the internal electrode layer 12.
  • the perovskite structure formed in the second region has Sn dissolved therein.
  • the formation of a perovskite structure containing Sn in solid solution suppresses the formation of a non-perovskite structure containing Ba, Ti, and Sn in the dielectric layer containing Ba, Ti, and Sn, which tends to relatively suppress a decrease in the proportion of the region composed of the perovskite structure.
  • the Sn dissolved in the perovskite structure formed in the second region may be dissolved in either the A element site (e.g., the Ba site) or the B element site (e.g., the Ti site), or may be dissolved in both.
  • the A element site e.g., the Ba site
  • the B element site e.g., the Ti site
  • Sn may be dissolved in the Ti site in the perovskite structure containing Ba and Ti formed in the second region.
  • the presence of the second region can be confirmed, for example, by performing a combination of TEM observation and EDX analysis on the region including the interface between the dielectric layer 11 and the internal electrode layer 12 in a cross section of the ceramic body 10 in the stacking direction.
  • TEM observation may be performed using the HAADF-STEM method described above.
  • Figure 2 is a schematic diagram of a TEM image of a region including the interface between the dielectric layer 11 and the internal electrode layer 12 in a cross section of the ceramic body 10 in the stacking direction.
  • An interface BL exists between the dielectric layer 11 and the internal electrode layer 12.
  • a first region M where Sn is dissolved exists in the internal electrode layer 12 near the interface BL with the dielectric layer 11.
  • An alloy containing Sn may be formed in the first region M. Elements other than Sn may also be dissolved in the first region M.
  • the direction indicated by the arrow in Figure 2 is the stacking direction L of the ceramic body 10.
  • the first region M is a region located near the interface BL, and may be, for example, a region located within several tens of nanometers of the interface BL in the stacking direction L of the ceramic body 10, or may be, for example, a region located within 10 nm of the interface BL.
  • the length (width) of the first region M in the stacking direction L may be, for example, 10 nm or less.
  • the first region M may be a region in contact with the dielectric layer 11, or may be a region not in contact with the dielectric layer 11.
  • the tin dissolved in the first region M may be, for example, located within several tens of nanometers of the interface BL in the stacking direction L of the ceramic body 10, or may be, for example, located within 10 nm of the interface BL.
  • a second region N is formed on the dielectric layer 11 side, contacting the internal electrode layer 12.
  • the perovskite structure formed in the second region N contains Sn as a solid solution.
  • the second region N may be formed over the entire interface BL between the dielectric layer 11 and the internal electrode layer 12, or may be formed only in a portion of the interface BL between the dielectric layer 11 and the internal electrode layer 12.
  • the second region N may be present in only one location, or may be present separately in multiple locations. From the perspective of the proportion of the region consisting of the perovskite structure, the more locations where the second region N is present, the better.
  • the second region N may be a region located within a few nanometers of the interface BL in the stacking direction of the ceramic body 10, for example, within 2 nanometers of the interface BL.
  • the length (width) of the second region N in the stacking direction L may be 2 nanometers or less. When the length (width) of the second region N from the interface BL is expressed in terms of the number of atomic layers, it may correspond to 1 to 5 atomic layers.
  • the first region M and the second region N can be obtained by adjusting the manufacturing conditions of the ceramic body, such as the sintering conditions in the firing process (e.g., sintering temperature, sintering time, etc.).
  • the sintering conditions in the firing process e.g., sintering temperature, sintering time, etc.
  • a pre-sintered dielectric sheet containing Sn oxide is fired in a first firing process and a second firing process, and by firing the second firing process for a longer time than the first firing process, Sn that has diffused uniformly within the dielectric layer segregates near the interface, forming a region where Sn is dissolved near the interface on the internal electrode layer side, and Sn tends to be more easily diffused into the dielectric layer while maintaining the perovskite structure.
  • the perovskite structure with Sn dissolved therein may be formed in a region other than the second region.
  • the perovskite structure with Sn dissolved therein may be formed in the entirety or part of the dielectric layer 11.
  • the dielectric layer 11 may further contain at least one element selected from the group consisting of Ni, manganese (Mn), magnesium (Mg), silicon (Si), aluminum (Al), vanadium (V), and rare earth elements.
  • the rare earth elements may include at least one element selected from the group consisting of scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).
  • the rare earth elements preferably include Dy.
  • the dielectric layer 11 contains a rare earth element
  • various properties such as high-temperature accelerated lifetime and temperature characteristics of dielectric constant tend to be improved.
  • BaTiO3 may contain many oxygen vacancies generated during the firing process. These oxygen vacancies serve as electrical charge pathways, which may reduce insulation resistance.
  • a rare earth element is added to the dielectric layer, it tends to dissolve in the Ba and Ti sites of the BaTiO3 -based compound.
  • the dissolved rare earth element functions as a donor or acceptor, preventing the migration of oxygen vacancies, resulting in increased insulation resistance and a tendency for high-temperature accelerated lifetime to be improved.
  • the dielectric layer may contain one type of rare earth element or a combination of multiple types of rare earth elements.
  • the rare earth element may be contained only in the BaTiO3 -based compound, which is the main component, or may be contained at grain boundaries, triple points, etc.
  • the dielectric layer 11 When the dielectric layer 11 contains Dy, Dy tends to dissolve easily in the A element site or B element site of the perovskite structure. As shown in FIG. 2 , the dielectric layer 11 includes crystal grains G of a BaTiO 3 -based compound, and grain boundaries GB are formed. Dy tends to dissolve easily in the Ba site or Ti site of the BaTiO 3 -based compound in the portion (shell portion) adjacent to the grain boundary GB. Furthermore, in the portion (shell portion) adjacent to the grain boundary GB of the crystal grain G present in the portion adjacent to the interface BL, Dy tends to dissolve more easily in the Ti site than in the Ba site. Furthermore, in the portion (shell portion) adjacent to the grain boundary GB of the crystal grain G present near the center inside the dielectric layer 11, away from the interface BL, Dy tends to dissolve more easily in the Ba site than in the Ti site.
  • a Dy segregation phase may be present inside the dielectric layer 11 in a portion in contact with the internal electrode layer 12.
  • the Dy segregation phase is generated when Dy that is not dissolved in the BaTiO3 -based compound during the firing process segregates at the interface.
  • the reliability of the multilayer ceramic capacitor 100 tends to be improved.
  • the multiple internal electrode layers 12 include a first internal electrode layer 12a and a second internal electrode layer 12b.
  • the first internal electrode layer 12a has an opposing electrode portion that faces the second internal electrode layer 12b across the dielectric layer 11, and an extraction electrode portion that extends from the opposing electrode portion to the first end face 13a of the ceramic body 10.
  • the second internal electrode layer 12b has an opposing electrode portion that faces the first internal electrode layer 12a across the dielectric layer 11, and an extraction electrode portion that extends from the opposing electrode portion to the second end face 13b of the ceramic body 10.
  • a single capacitor is formed by the first internal electrode layer 12a and the second internal electrode layer 12b facing each other with the dielectric layer 11 interposed therebetween.
  • the multilayer ceramic capacitor 100 can be thought of as multiple capacitors connected in parallel via the first external electrode 14a and second external electrode 14b described below.
  • the multilayer ceramic capacitor 100 further includes a first external electrode 14a and a second external electrode 14b.
  • the first external electrode 14a is formed on the first end surface 13a of the ceramic body 10 so as to be electrically connected to the first internal electrode layer 12a.
  • the first external electrode 14a extends from the first end surface 13a to the first and second main surfaces and the first and second side surfaces.
  • the second external electrode 14b is formed on the second end surface 13b of the ceramic body 10 so as to be electrically connected to the second internal electrode layer 12b.
  • the second external electrode 14b extends from the second end surface 13b to the first and second main surfaces and the first and second side surfaces.
  • the first external electrode 14a and the second external electrode 14b each have, for example, a base electrode layer and a plating layer disposed on the base electrode layer.
  • the base electrode layer includes, for example, at least one selected from a sintered body layer, a conductive resin layer, and a metal thin film layer.
  • the sintered body layer is formed by firing a paste containing glass powder and metal powder, and includes a glass portion and a metal portion.
  • the glass that constitutes the glass portion include B 2 O 3 —SiO 2 —BaO-based glasses.
  • the metal that constitutes the metal portion include at least one metal selected from Ni, Cu, Ag, and the like, or an alloy containing such a metal.
  • the sintered body layer may be formed of multiple layers made of different components. Furthermore, in the manufacturing method described below, the sintered body layer may be fired simultaneously with the ceramic body 10, or may be fired after the ceramic body 10 has been fired.
  • the conductive resin layer includes conductive particles, such as metal fine particles, and a resin portion.
  • the metal that makes up the metal fine particles can be at least one selected from Ni, Cu, Ag, etc., or an alloy containing such a metal.
  • the resin that makes up the resin portion can be an epoxy-based thermosetting resin, etc.
  • the conductive resin layer can be formed from multiple layers of different components.
  • the metal thin film layer is formed by a thin film formation method such as sputtering or vapor deposition, and is a layer of metal fine particles deposited to a thickness of 1 ⁇ m or less.
  • the metal constituting the metal thin film layer can be at least one selected from the group consisting of Ni, Cu, Ag, and Au, or an alloy containing such a metal.
  • the metal thin film layer may be formed from multiple layers of different components.
  • the metal constituting the plating layer may be at least one selected from the group consisting of Ni, Cu, Ag, Au, and Sn, or an alloy containing such a metal.
  • the plating layer may also be formed of multiple layers made of different components.
  • first external electrode 14a and the second external electrode 14b may each be a plating layer that is provided directly on the ceramic body 10 and directly connected to the corresponding internal electrode layer described above.
  • the manufacturing method of the multilayer ceramic capacitor 100 may include a lamination process of laminating a plurality of mother sheets, each including a pre-fired dielectric sheet having an internal electrode pattern formed thereon, to obtain a pre-fired ceramic body, a first firing process of firing the pre-fired ceramic body, and a second firing process of further firing the ceramic body after the first firing process.
  • the pre-fired dielectric sheet is a precursor of the dielectric layer and contains the main component raw material and additive component raw material of the dielectric layer, as well as Sn oxide.
  • the pre-fired dielectric sheet can be produced by any known method, without any particular limitation.
  • the main component raw material is mixed with the additive component raw material to produce the dielectric raw material, a binder and a solvent are added to and mixed with the resulting dielectric raw material to prepare a dielectric layer-forming slurry, and the resulting dielectric layer-forming slurry is then molded into the pre-fired dielectric sheet.
  • Sn oxide can be added to either or both of the dielectric raw material and the dielectric layer-forming slurry.
  • the dielectric layer forming slurry is formed into a sheet on a carrier film using a die coater, gravure coater, or microgravure coater, to form a pre-fired dielectric sheet.
  • a mother sheet is formed. Specifically, a conductive paste is printed in a predetermined pattern on the pre-fired dielectric sheet using a method such as screen printing or gravure printing, thereby forming a mother sheet with the predetermined conductive pattern on the pre-fired dielectric sheet.
  • pre-fired dielectric sheets without conductive patterns are also prepared as mother sheets.
  • the mother sheets are stacked. Specifically, a predetermined number of mother sheets that do not have a conductive pattern formed thereon and that form the outer layer portion are stacked, and then multiple mother sheets that have a conductive pattern formed thereon and that form the inner layer portion are stacked on top of these, and then a predetermined number of mother sheets that do not have a conductive pattern formed thereon and that form the outer layer portion are stacked on top of these, thereby forming a mother sheet group.
  • the mother laminate is divided. Specifically, the mother laminate is divided into a matrix by press-cutting or dicing, and is separated into a plurality of pre-fired ceramic bodies.
  • the pre-fired ceramic bodies may be barrel-polished.
  • the pre-fired ceramic body is fired.
  • the firing temperature in the first firing step is set appropriately depending on the type of starting material, and may be, for example, a temperature higher than 1100°C or 1200°C or higher.
  • the firing temperature in the first firing step may be, for example, a temperature lower than 1300°C.
  • the firing time in the first firing step may be, for example, 1 minute or more and 30 minutes or less.
  • the first firing step may be carried out in a reducing atmosphere.
  • the binder components Before firing in the first firing step, the binder components may be burned by heating in an inert gas (e.g., nitrogen) atmosphere at a temperature lower than the firing temperature, for example, a temperature of 500°C or less.
  • an inert gas e.g., nitrogen
  • the ceramic body is further fired after the first firing step.
  • the firing time in the second firing step is longer than that in the first firing step.
  • the firing time in the second firing step may, for example, exceed 30 minutes, may be 60 minutes or more, or may be 6 hours or less.
  • the firing temperature in the second firing step may be lower than that in the first firing step.
  • the firing temperature in the second firing step may be, for example, less than 1100°C, or 1000°C or less.
  • the firing temperature in the second firing step may be, for example, 900°C or more.
  • a base electrode layer is formed on the surface of the ceramic body, and then a plating layer is formed by electroplating to cover the base electrode layer.
  • the multilayer ceramic capacitor 100 of the present disclosure is manufactured.
  • the additive component raw materials were weighed out so that 1 molar part of dysprosium oxide ( Dy2O3 ), 1 molar part of nickel oxide (NiO), and 0.5 molar parts of silicon oxide ( SiO2 ) were contained per 100 molar parts of titanium (Ti) in the main component.
  • Tin oxide ( SnO2 ) was further compounded per 100 molar parts of titanium (Ti) in the main component in the amounts shown in Table 1. Note that no tin oxide ( SnO2 ) was compounded in Samples 1, 6, and 11.
  • the obtained powder of the additive component raw material was then blended with water and the main component raw material powder, mixed for a certain period of time using a ball mill, dried, and then dry-pulverized to obtain a dielectric raw material powder.
  • a polyvinyl butyral binder and ethanol were added to the obtained dielectric raw material powder, and the mixture was wet mixed using a ball mill to prepare a slurry.
  • the obtained slurry was formed into a sheet using the doctor blade method to obtain a pre-fired dielectric sheet.
  • the obtained pre-fired dielectric sheet had a thickness of 0.6 to 1.2 ⁇ m.
  • a conductive paste was printed in a specified pattern on the surface of the resulting pre-fired dielectric sheet to form an internal electrode pattern.
  • the conductive paste was made by adding a polyvinyl butyral binder and ethanol to nickel (Ni) powder and wet mixing it using a ball mill.
  • the resulting laminated chip was heated to 280°C in a nitrogen ( N2 ) atmosphere to burn off the binder.
  • the laminated chip from which the binder had been burned was then fired in a reducing atmosphere at 1200°C for 2 minutes, during which the firing timing of the internal electrode pattern and the pre-fired dielectric sheet was shifted to form a heterogeneous phase.
  • the laminated chip was then further fired at 1000°C for 300 minutes.
  • a copper (Cu) paste containing a B 2 O 3 —SiO 2 —BaO-based glass frit was applied to both end surfaces of the fired laminated chip, and baked at 800°C in a nitrogen (N 2 ) atmosphere to form external electrodes electrically connected to the internal electrode layers.
  • the thickness of each dielectric layer in the internal layer portion of the resulting multilayer ceramic capacitor was 0.33 to 0.60 ⁇ m.
  • the thickness of each internal electrode layer was 0.45 ⁇ m.
  • the microstructure near the interface between the dielectric layer and the internal electrode layer of the multilayer ceramic capacitor was observed with a TEM under the following conditions.
  • TEM observation The interfaces between the dielectric layers and internal electrode layers of a multilayer ceramic capacitor were observed using a high-angle annular dark-field scanning transmission electron microscope (HAADF-STEM). For the observation, samples were prepared by thin-film processing using the FIB method.
  • HAADF-STEM high-angle annular dark-field scanning transmission electron microscope
  • Figure 3 shows a TEM observation image of Sample 3.
  • Figure 3A is a TEM observation image near the interface between the internal electrode layer and the dielectric layer.
  • Figure 3B is an elemental mapping image of Sn in Figure 3A. As shown in Figure 3A, it was observed that a perovskite structure was formed in the region of the dielectric layer in contact with the internal electrode layer. As shown in Figure 3B, a region (first region) where Sn was dissolved was observed on the internal electrode layer side. Although not shown, segregation of Dy was confirmed on the dielectric layer side using a similar method.
  • Figure 4A is an elemental mapping image of Ti, and as shown in Figure 4C, it was observed that Sn was dissolved in the Ti site.
  • Example 16 The same operation as in Example 2 of JP-A-2022-143403 was carried out to prepare a multilayer ceramic capacitor of Example 16. Specifically, the amounts of the additive component raw materials used in the production of the above-mentioned sample 1 were weighed out so that, relative to 100 molar parts of titanium (Ti) in the main component, 0.75 molar parts of dysprosium oxide (Dy 2 O 3 ), 1 molar part of magnesium oxide (MgO), 0.2 molar parts of manganese oxide (MnO), and 1 molar part of silicon oxide (SiO 2 ) were used.
  • Ti titanium
  • Dy 2 O 3 dysprosium oxide
  • MgO magnesium oxide
  • MnO manganese oxide
  • SiO 2 silicon oxide
  • the obtained laminated chip was heated to 350°C in a nitrogen (N 2 ) atmosphere to burn off the binder, and then fired at 1200°C for 20 minutes in a reducing atmosphere of H 2 -N 2 -H 2 O gas with an oxygen partial pressure of 10 -10 to 10 -12 MPa at a temperature rise rate of 50°C to 100/min, during which the firing timing of the internal electrode pattern and the green sheet was shifted to form a heterogeneous phase.
  • N 2 nitrogen
  • the obtained element part was heated to 350°C in a reducing atmosphere of H 2 -N 2 -H 2 O gas with an oxygen partial pressure of 10 -10 to 10 -12 MPa at a temperature rise rate of 50°C to 100/min, during which the firing timing of the internal electrode pattern and the green sheet was shifted to form a heterogeneous phase.
  • a multilayer ceramic capacitor was fabricated in the same manner as in Sample 1, except that the sample was annealed in an atmosphere of 1050° C. for 30 minutes under a pressure of 100 MPa. The results are shown in Table 2.
  • samples 2-5, 7-10, and 12-15 exhibited high reliability and dielectric constant. Furthermore, samples 3-5, 8-10, and 13-15, which also contained Dy segregation phases, exhibited even higher reliability.
  • the multilayer ceramic capacitor of the present disclosure includes a ceramic element body in which multiple dielectric layers and multiple internal electrode layers are alternately stacked.
  • the dielectric layers contain ceramic as a primary component.
  • the ceramic contains barium and titanium.
  • the dielectric layers further contain tin.
  • the internal electrode layers contain nickel as a primary component.
  • the internal electrode layers have a first region in which tin is dissolved, at least near the interface with the dielectric layer.
  • the dielectric layers have a second region in which a perovskite structure containing barium and titanium is formed. The second region is in contact with the internal electrode layers.
  • the perovskite structure in the second region contains tin as a solid solution.
  • the thickness of the internal electrode layer is 0.4 ⁇ m or less.
  • the multilayer ceramic capacitor described in any one of Items 1 to 6 further contains a rare earth element.

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  • Ceramic Capacitors (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)

Abstract

La présente divulgation concerne un condensateur céramique multicouche (100). Un condensateur céramique multicouche (100) selon la présente invention comprend un élément céramique (10) dans lequel une pluralité de couches diélectriques (11) et une pluralité de couches d'électrode interne (12) sont stratifiées en alternance. La couche diélectrique (11) contient de la céramique en tant que composant principal, la céramique contient du baryum et du titane, et la couche diélectrique (11) contient en outre de l'étain. La couche d'électrode interne (12) contient du nickel en tant que composant principal. La couche d'électrode interne (12) comprend, à proximité d'une interface avec au moins la couche diélectrique (11), une première région dans laquelle l'étain est dissous, et la couche diélectrique comprend une seconde région dans laquelle une structure de pérovskite contenant du baryum et du titane est formée. La seconde région est en contact avec la couche d'électrode interne (12), et l'étain est dissous dans la structure pérovskite dans la seconde région.
PCT/JP2025/014130 2024-05-27 2025-04-09 Condensateur céramique multicouche Pending WO2025248979A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2024085426 2024-05-27
JP2024-085426 2024-05-27

Publications (1)

Publication Number Publication Date
WO2025248979A1 true WO2025248979A1 (fr) 2025-12-04

Family

ID=97870070

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2025/014130 Pending WO2025248979A1 (fr) 2024-05-27 2025-04-09 Condensateur céramique multicouche

Country Status (1)

Country Link
WO (1) WO2025248979A1 (fr)

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