WO2024247326A1 - 電子部品 - Google Patents

電子部品 Download PDF

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Publication number
WO2024247326A1
WO2024247326A1 PCT/JP2023/044667 JP2023044667W WO2024247326A1 WO 2024247326 A1 WO2024247326 A1 WO 2024247326A1 JP 2023044667 W JP2023044667 W JP 2023044667W WO 2024247326 A1 WO2024247326 A1 WO 2024247326A1
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WIPO (PCT)
Prior art keywords
base electrode
electrode
copper particles
element body
electronic component
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Ceased
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PCT/JP2023/044667
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English (en)
French (fr)
Japanese (ja)
Inventor
紀行 大川
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to JP2024529434A priority Critical patent/JP7715289B2/ja
Publication of WO2024247326A1 publication Critical patent/WO2024247326A1/ja
Priority to US19/059,361 priority patent/US20250191846A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F27/00—Details of transformers or inductances, in general
    • H01F27/28—Coils; Windings; Conductive connections
    • H01F27/29—Terminals; Tapping arrangements for signal inductances
    • 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
    • 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
    • H01G4/002—Details
    • H01G4/228—Terminals
    • H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
    • H01G4/2325—Terminals electrically connecting two or more layers of a stacked or rolled capacitor characterised by the material of the terminals
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/05—Manufacture of multilayered piezoelectric or electrostrictive devices, or parts thereof, e.g. by stacking piezoelectric bodies and electrodes
    • H10N30/057—Manufacture of multilayered piezoelectric or electrostrictive devices, or parts thereof, e.g. by stacking piezoelectric bodies and electrodes by stacking bulk piezoelectric or electrostrictive bodies and electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/06—Forming electrodes or interconnections, e.g. leads or terminals
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/87—Electrodes or interconnections, e.g. leads or terminals

Definitions

  • This disclosure relates to electronic components.
  • the electronic component described in Patent Document 1 has an element body, an internal electrode, and an external electrode.
  • the internal electrode is located inside the element body.
  • the external electrodes include a first electrode, a second electrode, and a third electrode.
  • the first electrode covers a part of the outer surface of the element body.
  • the main component of the first electrode is Cu.
  • the second electrode covers the outer surface of the first electrode.
  • the main component of the second electrode is Ag-Pd.
  • the third electrode covers the outer surface of the second electrode.
  • the main components of the third electrode are Ag and synthetic resin.
  • the electronic component described in Patent Document 1 is subject to external mechanical shocks and thermal shocks due to temperature changes. This can cause cracks in the body of the electronic component.
  • the third electrode contains a synthetic resin, and the resin component can suppress impacts on the body.
  • the silver component of the third electrode is prone to elution in high temperature and humidity environments. As a result, the eluted silver component may come into contact with other elements and cause migration. Therefore, there is a demand for technology that suppresses impacts on the body while suppressing migration.
  • one aspect of the present disclosure is an electronic component comprising an element body and an external electrode that covers a portion of the outer surface of the element body and does not contain silver components, the external electrode having a base electrode that covers the outer surface of the element body, the base electrode containing copper particles and a synthetic resin, and when the base electrode is divided into a first portion located on the element body side and a second portion located on the opposite side to the element body, the average diameter of the copper particles in the second portion is larger than the average diameter of the copper particles in the first portion.
  • the external electrode does not contain silver components. Therefore, with the above configuration, migration can be suppressed compared to when the external electrode contains silver components. On the other hand, since the grain size of the copper particles in the second portion is relatively large, the occurrence of cracks in the element can also be suppressed.
  • FIG. 1 is a perspective view of an electronic component.
  • FIG. 2 is a side view of the electronic component.
  • FIG. 3 is a cross-sectional view taken along line 3-3 of FIG.
  • FIG. 4 is a schematic cross-sectional view of a first external electrode of an electronic component.
  • FIG. 5 is an enlarged view of a first base electrode of the electronic component.
  • FIG. 6 is a schematic diagram of copper particles in a specific cross section of a first base electrode in an electronic component.
  • FIG. 7 is a flow chart illustrating a method for manufacturing an electronic component.
  • the electronic component 10 is a multilayer ceramic capacitor.
  • the electronic component 10 includes an element body 20.
  • the element body 20 is substantially rectangular prism-shaped and has a central axis CA.
  • an axis extending along the central axis CA is defined as a first axis X.
  • one of the axes perpendicular to the first axis X is defined as a second axis Y.
  • an axis perpendicular to the first axis X and the second axis Y is defined as a third axis Z.
  • one of the directions along the first axis X is defined as a first positive direction X1, and the direction along the first axis X opposite to the first positive direction X1 is defined as a first negative direction X2.
  • one of the directions along the second axis Y is defined as a second positive direction Y1, and the direction along the second axis Y opposite to the second positive direction Y1 is defined as a second negative direction Y2.
  • one of the directions along the third axis Z is defined as a third positive direction Z1, and the direction along the third axis Z opposite to the third positive direction Z1 is defined as a third negative direction Z2.
  • the outer surface 21 of the element body 20 has six flat surfaces.
  • the "surface” of the element body 20 here refers to a surface that can be observed when the entire element body 20 is observed. In other words, even if there are minute irregularities or steps that cannot be seen unless a part of the element body 20 is magnified and observed with a microscope, the surface is expressed as a flat surface or a curved surface.
  • the six flat surfaces face in different directions.
  • the six flat surfaces are broadly divided into a first end surface 22A facing the first positive direction X1, a second end surface 22B facing the first negative direction X2, and four side surfaces 22C.
  • the four side surfaces 22C are a surface facing the third positive direction Z1, a surface facing the third negative direction Z2, a surface facing the second positive direction Y1, and a surface facing the second negative direction Y2, respectively.
  • the boundary portions between two adjacent flat surfaces and between three adjacent flat surfaces of the outer surface 21 of the element body 20 are curved. In other words, the corners of the element body 20 are rounded and chamfered.
  • the element body 20 has a dimension along the first axis X that is greater than the dimension along the third axis Z and the dimension along the second axis Y.
  • the material of the element body 20 is a dielectric ceramic. Specifically, the material of the element body 20 is mainly composed of BaTiO3 .
  • the material of the element body 20 may also be mainly composed of CaTiO3 , SrTiO3 , CaZrO3 , etc.
  • the material of the element body 20 may also contain a Mn compound, a Co compound, a Si compound, a rare earth compound, etc. as a secondary component.
  • the electronic component 10 has four first internal electrodes 41 and four second internal electrodes 42.
  • the first internal electrodes 41 and the second internal electrodes 42 are located inside the element body 20.
  • the material of the first internal electrode 41 is a conductive material.
  • the material of the first internal electrode 41 is Ni.
  • the material of the first internal electrode 41 may further include a metal such as Ni, Cu, Ag, Au, Pt, Sn, Pd, or an alloy containing these metals.
  • the material of the second internal electrode 42 is the same as the material of the first internal electrode 41.
  • the first internal electrode 41 has a rectangular plate shape.
  • the main surface of the first internal electrode 41 is perpendicular to the second axis Y.
  • the second internal electrode 42 has the same rectangular plate shape as the first internal electrode 41.
  • the main surface of the second internal electrode 42 is perpendicular to the second axis Y, similar to the first internal electrode 41.
  • the dimension of the first internal electrode 41 in the direction along the first axis X is smaller than the dimension of the element body 20 in the direction along the first axis X. Also, as shown in FIG. 1, the dimension of the first internal electrode 41 in the direction along the third axis Z is approximately two-thirds of the dimension of the element body 20 in the direction along the third axis Z. The dimensions of the second internal electrode 42 in each direction are the same as those of the first internal electrode 41.
  • the first internal electrodes 41 and the second internal electrodes 42 are positioned alternately in the direction along the second axis Y. That is, a total of eight internal electrodes are arranged alternately in the order of the first internal electrodes 41 and the second internal electrodes 42 from the side surface 22C facing the second positive direction Y1 toward the second negative direction Y2. In this embodiment, the distance between each internal electrode in the direction along the second axis Y is equal.
  • the four first internal electrodes 41 and the four second internal electrodes 42 are all located in the center of the element body 20 in the direction along the third axis Z.
  • the first internal electrodes 41 are located closer to the first positive direction X1.
  • the second internal electrodes 42 are located closer to the first negative direction X2.
  • the end of the first internal electrode 41 on the first positive direction X1 side is approximately aligned with the end of the element body 20 on the first positive direction X1 side. Therefore, the end of the first internal electrode 41 on the first positive direction X1 side is exposed from the first end surface 22A of the element body 20.
  • the end of the first internal electrode 41 on the first negative direction X2 side is located inside the element body 20 and does not reach the end of the element body 20 on the first negative direction X2 side.
  • the end of the second internal electrode 42 on the first negative direction X2 side is approximately aligned with the end of the element body 20 on the first negative direction X2 side. Therefore, the end of the second internal electrode 42 on the first negative direction X2 side is exposed from the second end face 22B of the element body 20.
  • the end of the second internal electrode 42 on the first positive direction X1 side is located inside the element body 20 and does not reach the end of the element body 20 on the first positive direction X1 side.
  • the electronic component 10 has a first external electrode 61 and a second external electrode 62.
  • the first external electrode 61 and the second external electrode 62 are conductive as a whole.
  • the first external electrode 61 and the second external electrode 62 do not contain silver components.
  • does not contain silver components means that a small amount of silver components is allowed to be mixed into each external electrode during the manufacturing process. For example, if the atomic percentage of silver atoms relative to all atoms constituting each external electrode is less than 1 atm%, it is considered that "the external electrode does not contain silver components.” This is because if the atomic percentage of silver atoms is less than 1 atm%, no significant migration that would affect the characteristics of the electronic component 10 occurs.
  • the first external electrode 61 has a first base electrode 61A, a first mixed layer 61B, and a first metal layer 61C. Note that the first mixed layer 61B is indicated by a thick line in Fig. 3 .
  • the first base electrode 61A covers a portion of the outer surface 21 of the element body 20, including the first end face 22A.
  • the first base electrode 61A is a five-sided electrode that covers the first end face 22A of the element body 20 and portions of the four side faces 22C in the first positive direction X1.
  • the first base electrode 61A is made of copper and glass.
  • the first base electrode 61A is a sintered body. Details of the first base electrode 61A will be described later.
  • the first metal layer 61C covers the outer surface BD61A of the first base electrode 61A. A portion of the first metal layer 61C protrudes from the first base electrode 61A. Although not shown, the first metal layer 61C has a two-layer structure consisting of, in order from the first mixed layer 61B side, a nickel layer and a tin layer.
  • the first mixed layer 61B is located between the first base electrode 61A and the first metal layer 61C.
  • the first metal layer 61C covers the outer surface BD61A of the first base electrode 61A via the first mixed layer 61B. Details of this first mixed layer 61B will be described later.
  • the second external electrode 62 has a second base electrode 62A, a second mixed layer 62B, and a second metal layer 62C.
  • the second mixed layer 62B is indicated by a thick line.
  • the second base electrode 62A covers a portion of the outer surface 21 of the element body 20, including the second end face 22B.
  • the second base electrode 62A is a five-sided electrode that covers the second end face 22B of the element body 20 and portions of the four side faces 22C in the first negative direction X2.
  • the material of the second base electrode 62A is the same as the material of the first external electrode 61, that is, copper and glass.
  • the second base electrode 62A is a sintered body. Details of the second base electrode 62A will be described later.
  • the second metal layer 62C covers the outer surface BD62A of the second base electrode 62A. In addition, a portion of the second metal layer 62C protrudes from the second base electrode 62A. Although not shown, the second metal layer 62C has a two-layer structure, similar to the first metal layer 61C, consisting of a nickel layer and a tin layer, in that order from the second mixed layer 62B side.
  • the second mixed layer 62B is located between the second base electrode 62A and the second metal layer 62C.
  • the second metal layer 62C covers the outer surface BD62A of the second base electrode 62A via the second mixed layer 62B. Details of the second mixed layer 62B will be described later.
  • the second external electrode 62 does not reach the first external electrode 61 on the side surface 22C, and is disposed away from the first external electrode 61 in the direction along the first axis X. Furthermore, the first external electrode 61 and the second external electrode 62 are not stacked in the central portion in the direction along the first axis X on the side surface 22C of the element body 20. Note that in Figures 1 to 3, the first external electrode 61 and the second external electrode 62 are shown by two-dot chain lines.
  • the first base electrode 61A contains copper and silicon.
  • At least a portion of the copper in the first base electrode 61A is a spherical copper particle 63.
  • a spherical copper particle 63 As shown in FIG. 5, at least a portion of the copper in the first base electrode 61A is a spherical copper particle 63. Note that in FIG. 5, only some of the copper particles 63 are labeled with reference numerals. Also, in FIG. 5, each copper particle 63 is illustrated as being approximately circular, but it may be an elliptical or other irregularly shaped particle.
  • Silicone resin 64 is a polymer consisting of siloxane bonds and Si-C bonds.
  • the average value of the thickness H of the first base electrode 61A is about 700 nm.
  • the thickness H of the first base electrode 61A is the shortest distance from the outer surface BD61A of the first base electrode 61A to the outer surface 21 of the base body 20.
  • FIG. 4 illustrates the thickness H at one arbitrary point.
  • the copper particles 63 and the silicone resin 64 in the first base electrode 61A are omitted, and the first base electrode 61A is illustrated as an integrated electrode.
  • the average value of the thickness H of the first base electrode 61A is calculated as follows. First, an arbitrary cross section of the first base electrode 61A is photographed with an electron microscope.
  • a range in the direction along the outer surface BD61A of the first base electrode 61A is identified for the photographed image.
  • the cross-sectional area of the first base electrode 61A is calculated by image processing for a measurement range of at least 5 ⁇ m or more.
  • the average thickness H of the first base electrode 61A is calculated by dividing the calculated cross-sectional area of the first base electrode 61A in the measurement range by the length of the measurement range.
  • the outer surface BD61A of the first base electrode 61A is the boundary where chemical components contained only in the first metal layer 61C are no longer observed. In the above cross section, the outer surface BD61A of the first base electrode 61A roughly coincides with the interface that follows the edge of the copper particle 63 on the first metal layer 61C side.
  • the first base electrode 61A is divided into a first portion P1 located on the element body 20 side of the first base electrode 61A, and a second portion P2 located on the opposite side of the element body 20.
  • the position at which the first base electrode 61A is divided into two is the point at which the average value of the thickness H of the first base electrode 61A is divided into two.
  • the first portion P1 is in the range of approximately 350 nm from the outer surface 21 of the element body 20 toward the outer surface BD61A of the first base electrode 61A.
  • the first base electrode 61A has gaps PA between the copper particles 63, where no synthetic resin such as silicone resin 64 is present.
  • the proportion of gaps PA in the second portion P2 is greater than the proportion of gaps PA in the first portion P1.
  • the gaps PA are more numerous near the outer surface BD61A of the first base electrode 61A. Note that the gaps PA are shown diagrammatically in FIG. 4.
  • the proportion of voids PA in the second portion P2 and the proportion of voids PA in the first portion P1 are determined by the porosity measured as follows. First, the first portion P1 is observed in a square area with each side being 500 nm at a magnification of 200,000 or more using a transmission electron microscope. In that area, the total area of the voids PA, i.e., the areas without copper particles 63 and silicone resin 64, is calculated by image processing. The porosity is then calculated from the area ratio of the total area of the voids PA to the observed area. This process is repeated at four locations in the first portion P1, and the average value of the porosity in each area is taken as the proportion of voids PA in the first portion P1. In the same manner, the proportion of voids PA in the second portion P2 is calculated.
  • the average particle size of the copper particles 63 differs between the first portion P1 and the second portion P2. Specifically, the average particle size of the copper particles 63 in the first portion P1 is smaller than the average particle size of the copper particles 63 in the second portion P2. Specifically, the average particle size of the first portion P1 is 75 nm or less. The average particle size of the second portion P2 is 100 nm or more. Therefore, the ratio of the average particle size of the copper particles 63 in the second portion P2 to the average particle size of the copper particles 63 in the first portion P1 is 1.2 or more. Also, as a whole, the particle size of the copper particles 63 becomes smaller in the first base electrode 61A toward the element body 20 side.
  • the average value of the particle diameter of the copper particles 63 in the first portion P1 is determined as follows. First, an image of the first base electrode 61A is obtained with an electron microscope at a magnification range that includes the outer surface BD61A of the first base electrode 61A and the boundary on the outer surface 21 side of the element body 20. Then, in the image, the first portion P1 at a location that does not include the boundary with the outer surface 21 of the element body 20 and the position that bisects the first base electrode 61A is enlarged, and the contour of the copper particle 63 is obtained by image processing. Then, the area of one copper particle 63 is calculated. Then, a circle having the calculated area is assumed.
  • the diameter of the circle is calculated as the particle diameter of the copper particle 63. Then, the particle diameters of five or more copper particles 63 are calculated, and the average value is calculated. In this way, the average value of the particle diameters of the copper particles 63 is calculated in five or more images, and the average value of the average values obtained from these five images is set as the average value of the particle diameters of the copper particles 63 in the first portion P1. In the same manner, the average particle size of the copper particles 63 in the second portion P2 is calculated.
  • the first base electrode 61A is viewed in a specific cross section perpendicular to the outer surface BD61A.
  • the specific cross section at least some of the copper particles 63 have an elliptical shape. Note that in FIG. 6, only some of the copper particles 63 are labeled with reference numerals.
  • the flattening ratio of the elliptical copper particle 63 is 0.5 or less.
  • the flattening ratio is calculated as follows. First, the contour of the copper particle 63 is obtained by image processing using an electron microscope. The obtained image is analyzed, and half the length of the longest line segment among the line segments connecting the edges of one copper particle 63 is taken as the major axis. In addition, half the length of the line segment that is perpendicular to the major axis and connects the edges of the copper particle 63 is taken as the minor axis. When the major axis is a, the minor axis is b, and the flattening ratio is F, the flattening ratio is calculated based on the following formula 1.
  • the axis along the major axis is the major axis V1.
  • the axis along the minor axis is the minor axis V2 of the copper particle 63.
  • the acute angle Q between the major axis V1 of the elliptical copper particle 63 in the specific cross section and the axis L along the outer surface BD61A of the first base electrode 61A is 45 degrees or less. That is, the elliptical copper particle 63 is positioned such that the major axis V1 is along the outer surface BD61A of the first base electrode 61A as a whole.
  • the axis L along the outer surface BD61A of the first base electrode 61A is determined as follows. For the image acquired in the specific cross section, an approximate straight line is drawn to the outer surface BD61A of the first base electrode 61A. The approximate straight line can be obtained, for example, by the least squares method. Then, an axis along this approximate straight line is defined as an axis L along the outer surface BD61A of the first base electrode 61A.
  • the first mixed layer 61B and the second mixed layer 62B will be described below. Note that, although the first mixed layer 61B will be described below as a representative, the same applies to the second mixed layer 62B.
  • the first mixed layer 61B is located between the first base electrode 61A and the first metal layer 61C. Note that although the boundaries between the first base electrode 61A, the first mixed layer 61B, and the first metal layer 61C are virtually illustrated by solid lines, it may not be possible to clearly observe the boundaries.
  • the first mixed layer 61B is sufficiently small compared to the thickness H of the first base electrode 61A.
  • the thickness of the first mixed layer 61B is 10% or less of the thickness H of the first base electrode 61A.
  • the first mixed layer 61B contains a chemical component that is not contained in the first base electrode 61A and is contained in the first metal layer 61C.
  • the chemical component is a nickel component that is a component of the first metal layer 61C.
  • the first mixed layer 61B also contains a chemical component that is not contained in the first metal layer 61C and is contained in the first base electrode 61A.
  • the chemical component is a copper component and a silicone component that are components of the first base electrode 61A.
  • the components of the first mixed layer 61B do not include components other than the components of the first base electrode 61A and the components of the first metal layer 61C. That is, the first mixed layer 61B is a layer formed by mixing the first base electrode 61A and the first metal layer 61C.
  • the method for manufacturing electronic component 10 includes a laminate preparation step S11, a R-chamfering step S12, a conductor application step S13, a curing step S14, and a plating step S15.
  • a laminate is prepared.
  • the laminate at this stage is in a state before R-chamfering, and is a rectangular parallelepiped with six flat surfaces.
  • a plurality of ceramic sheets that will become the element body 20 are prepared.
  • the sheets are thin plates.
  • a conductive paste that will become the first internal electrode 41 is laminated on the sheets.
  • a ceramic sheet that will become the element body 20 is laminated on the paste.
  • a conductive paste that will become the second internal electrode 42 is laminated on the sheets. In this way, the ceramic sheets and the conductive paste are laminated alternately.
  • the laminated sheets are compressed in the stacking direction by a means such as a mold press.
  • the compressed sheet is then cut to a predetermined size to form an unfired laminate.
  • the unfired laminate is then fired at a high temperature to prepare the laminate.
  • the R-chamfering process S12 is performed.
  • the laminate prepared in the laminate preparation process S11 is R-chamfered. This process produces the base body 20 with R-chamfered corners.
  • the conductor application process S13 is performed.
  • a conductor paste is applied by a dip method to two locations: a portion of the first end face 22A of the element body 20 and a portion of the second end face 22B of the element body 20.
  • the conductor paste is applied so as to cover the entire first end face 22A and portions of the four side faces 22C.
  • the conductor paste is also applied so as to cover the entire second end face 22B and portions of the four side faces 22C.
  • the conductor paste contains a copper component and a silicon component.
  • the conductive paste is a complex ink.
  • the conductive paste of the complex ink is made as follows. First, an amine compound such as 2-ethylhexylamine is mixed with an alcohol amine such as 2-amino-2-methylpropanol. Then, a silicon component such as silicone resin is added at 0.001-10 wt% based on the weight of Cu alone. Then, a metal salt is further added and dissolved to make the conductive paste. In other words, the conductive paste contains a copper component and a silicon component. The sintering start temperature of the copper component is 170 degrees, and the hardening start temperature of the silicon component is 250 degrees.
  • the curing step S14 is performed. Specifically, in the curing step S14, the base body 20 to which the conductive paste has been applied is heated. In this embodiment, the base body 20 to which the conductive paste has been applied is heated in a nitrogen atmosphere. In the curing step S14, the heating is performed in two stages. In the first stage, the temperature of the nitrogen atmosphere is maintained within a range of 200 to 400 degrees. In the second stage, the temperature of the nitrogen atmosphere is maintained within a range of 300 to 700 degrees. This causes the conductive paste to be fired. In addition, the heating in the second stage causes the bonds of some of the chemical components in the synthetic resin contained in the conductive paste to break down, resulting in the generation of voids PA.
  • the copper particles 63 and the silicone resin 64 are formed as follows. First, sintering of the copper component contained in the first base electrode 61A and the second base electrode 62A begins. At the time when sintering of the copper component begins, the silicon component is not hardened and has fluidity. Therefore, the silicon component fills the gaps between the copper components. In addition, when sintering the copper component, sintering of the copper component begins from the surface side of the conductive paste. At this time, the small copper particles 63 are united into large copper particles 63 by Ostwald ripening. As a result, the average particle size of the copper particles 63 in the second portion P2 becomes larger than the average particle size of the copper particles 63 in the first portion P1.
  • the hardening start temperature of the silicon component is higher than the sintering start temperature of the copper component.
  • copper particles 63 are generated by sintering the copper component.
  • silicone resin 64 is generated by hardening the silicon component.
  • a mesh-like silicone resin 64 fills the gaps between the copper particles 63.
  • the plating step S15 is performed.
  • the first base electrode 61A and the second base electrode 62A are electroplated.
  • a first metal layer 61C is formed on the surface of the first base electrode 61A.
  • a second metal layer 62C is formed on the surface of the second base electrode 62A.
  • a part of the chemical components of the first metal layer 61C is mixed with the chemical components melted from the first base electrode 61A to form a first mixed layer 61B.
  • the second mixed layer 62B is electroplated with two types of metal, nickel and tin, to form a two-layer structure. In this manner, the electronic component 10 is formed.
  • the first external electrode 61 does not contain silver. Therefore, according to the above embodiment, migration can be suppressed compared to when the first external electrode 61 contains silver.
  • the average particle size of the copper particles 63 in the second portion P2 is larger than the average particle size of the copper particles 63 in the first portion P1. Due to the larger particle size of the copper particles 63 in the second portion P2, the number of copper particles 63 contained in the second portion P2 is smaller than that in the first portion P1. Therefore, in the second portion P2, the contact area between one copper particle 63 and other copper particles 63 is smaller than that in the first portion P1. As a result, the mechanical strength of the second portion P2 is lower than that of the first portion P1. Therefore, if an impact is applied to the electronic component 10, cracks are more likely to occur in the second portion P2 than in the first portion P1.
  • the second portion P2 plays a role in mitigating the effects of the impact by breaking itself. Therefore, when an impact acts on the electronic component 10, the second portion P2 absorbs the impact, so that cracks and the like are less likely to occur in the base body 20. Furthermore, the second portion P2 of the first base electrode 61A, which is farther from the element body 20, can provide the above-mentioned shock mitigation effect, so that the element body 20 is less susceptible to shock. In other words, according to the above embodiment, it is possible to suppress the occurrence of migration while suppressing shock to the element body 20.
  • the ratio of the average particle size of the copper particles 63 in the second portion P2 to the average particle size of the copper particles 63 in the first portion P1 is 1.2 or more. This configuration makes it easier to achieve the impact mitigation effect in the second portion P2.
  • the average particle size of the copper particles 63 in the second portion P2 is 100 nm or more.
  • the average particle size of the copper particles 63 in the second portion P2 is appropriately large, so that the contact area between the copper particles 63 is reduced. In other words, by deliberately reducing the mechanical strength of the second portion P2, the impact mitigation effect on the base body 20 can be further improved.
  • the average particle size of the copper particles 63 in the first portion P1 is 75 nm or less. In this configuration, the average particle size of the copper particles 63 in the first portion P1 is appropriately small, so that the contact area between the copper particles 63 increases. In other words, with the above configuration, the mechanical strength of the first portion P1 is ensured, thereby preventing cracks that occur in the second portion P2 from propagating to the entire first base electrode 61A, including the first portion P1.
  • the acute angle Q between the long axis V1 of the elliptical copper particle 63 in a specific cross section and the axis L along the outer surface BD61A of the first base electrode 61A is 45 degrees or less.
  • the copper particles 63 are oriented so that they are horizontally elongated in the direction along the outer surface BD61A of the first base electrode 61A. Cracks are likely to occur in the gaps between these copper particles 63. Therefore, if a crack occurs in the second portion P2, there is a high possibility that the crack will extend in the direction along the outer surface BD61A of the first base electrode 61A. Therefore, according to the above configuration, even if a crack occurs in the second portion P2, there is little risk that the crack will propagate to the first portion P1.
  • the proportion of voids PA in the second portion P2 is greater than the proportion of voids PA in the first portion P1. If an impact is applied to the first base electrode 61A, cracks are likely to occur starting from the voids PA. Therefore, with the above configuration, cracks are more likely to occur in the second portion P2 than in the first portion P1. As a result, the impact mitigation effect of the second portion P2 can be reliably obtained.
  • the first mixed layer 61B contains chemical components that are not included in the first base electrode 61A but are included in the first metal layer 61C.
  • the first mixed layer 61B also contains chemical components that are not included in the first metal layer 61C but are included in the first base electrode 61A.
  • the first mixed layer 61B is a mixture of the chemical components of the first base electrode 61A and the first metal layer 61C near the boundary between them.
  • the electronic component 10 is not limited to a multilayer ceramic capacitor.
  • the electronic component 10 may be a piezoelectric component, a thermistor, an inductor, or the like.
  • the material of the element body 20 may be a dielectric material, a piezoelectric material, a magnetic material such as ferrite, or a composite material of synthetic resin and metal.
  • the shape of the element body 20 is not limited to the example of the above embodiment.
  • the element body 20 may be a polygonal column shape other than a rectangular column shape having a central axis CA.
  • the element body 20 may also be the core of a wire-wound inductor component.
  • the core may have a so-called drum core shape.
  • the core may have a cylindrical winding core portion and flange portions provided at each end of the winding core portion.
  • the boundary portion between adjacent flat surfaces of the outer surface 21 of the element body 20 does not have to be chamfered. In this case, no curved surface exists at the boundary portion.
  • the first internal electrodes 41 and the second internal electrodes 42 may have any shape as long as they can ensure electrical conduction with the corresponding first external electrodes 61 and second external electrodes 62. In addition, the number of first internal electrodes 41 and second internal electrodes 42 does not matter and may be less than four or more than four.
  • the first external electrode 61 may not have the first mixed layer 61B. That is, the boundary between the first base electrode 61A and the first metal layer 61C may be clearly separated.
  • the first metal layer 61C may cover at least a portion of the first base electrode 61A.
  • the average value of the thickness H of the first base electrode 61A is not limited to the example of the above embodiment.
  • the overall thickness of the first external electrode 61, including the first base electrode 61A, can be designed taking into account the mechanical strength required of the electronic component 10, etc.
  • the configuration related to the first metal layer 61C in the first external electrode 61 may be omitted.
  • the material of the first metal layer 61C is not limited to the example of the above embodiment.
  • the first metal layer 61C may be only nickel, only tin, or may contain other materials besides silver.
  • the first metal layer 61C may be copper, gold, palladium, etc.
  • the synthetic resin is not limited to silicone resin 64.
  • the synthetic resin may be a synthetic resin containing silicon, such as a silicone oligomer. In this way, when the synthetic resin contains silicon, the first base electrode 61A is likely to become a dense film.
  • the synthetic resin contained in the first base electrode 61A may contain nitrogen.
  • the synthetic resin may be a synthetic resin containing nitrogen, such as urethane, epoxy, polyimide, polyimideamide, or polyamide. In this way, when the synthetic resin contains nitrogen, the heat resistance of the first base electrode 61A is improved.
  • the synthetic resin is not limited to resins containing nitrogen and silicon, but may be resins such as acrylic, alkyd, polyester, or other synthetic resins.
  • the first base electrode 61A may use as its synthetic resin a combination of these synthetic resins containing nitrogen, synthetic resins containing silicon, and other synthetic resins.
  • the first base electrode 61A may use as its synthetic resin a synthetic resin that contains silicon and nitrogen in one type of synthetic resin.
  • the average particle size of the copper particles 63 in the first portion P1 may be greater than 75 nm.
  • the average particle size of the copper particles 63 in the second portion P2 may be less than 100 nm.
  • the ratio of the average particle size of the copper particles 63 in the second portion P2 to the average particle size of the copper particles 63 in the first portion P1 may be less than 1.2.
  • the ratio of the average particle size of the copper particles 63 in the second portion P2 to the average particle size of the copper particles 63 in the first portion P1 is preferably 1.4 or more, and more preferably 1.6 or more.
  • the acute angle Q between the long axis V1 of the copper particle 63 and the axis L along the outer surface BD61A of the first base electrode 61A may be greater than 45 degrees.
  • the flattening ratio of the copper particle 63 may be greater than 0.5.
  • the copper particles 63 may all be substantially circular.
  • the proportion of the void PA in the second portion P2 may be the same as or smaller than the proportion of the void PA in the first portion P1. Also, in the above embodiment, the first base electrode 61A may not have a void PA.
  • the manufacturing process of the electronic component 10 in the above embodiment is not limited to the example in the above embodiment.
  • the element body 20 may be subjected to a process such as physical polishing.
  • the method of applying the conductive paste is not limited to the example in the above embodiment.
  • the paste may be applied by printing, or may be applied by an inkjet method or the like.
  • the heating may be performed three or more times, or may be performed only once.
  • the sintering start temperature of the copper component and the hardening start temperature of the silicon component of the conductive paste are not limited to the examples in the above embodiment.
  • the first metal layer 61C may be formed by another method such as sputtering.
  • the conductive paste may be nano-ink.
  • nano-ink it is prepared as follows. Nano-metal powder is dispersed in a solvent containing cellosolves, carbitols, hydrocarbons, aromatics, etc. Then, various silicone-modified resins, silicone resins, sol-gel materials, etc. are added in an amount of 0.001-10 wt % relative to the weight of Cu alone.
  • the conductive paste of nano-ink may be prepared in this manner, or a different method may be used.
  • the material when the conductive paste is a complex ink is not limited to the example of the above embodiment.
  • the amine compound may be any of primary amines, secondary amines, and tertiary amines, and the number of N atoms is not limited.
  • it may be a primary amine such as octylamine or hexylamine, a secondary amine such as di-n-butylamine, or a tertiary amine such as N,N-dimethylhexylamine.
  • the amine compound may also be an alcohol amine or diamine, and the positional relationship between the N atom and the OH group is not specified as ⁇ , ⁇ , ⁇ , etc.
  • the number of N and O atoms in one molecule is not particularly limited.
  • it may be an ⁇ -hydroxyamine such as 2-dimethylaminoethanol or 2-ethylaminoethanol, or a ⁇ -hydroxyamine such as 3-amino-1-propanol or 4-amino-2-butanol.
  • it may be a diamine such as ethylenediamine, or a cyclic diamine such as piperazine.
  • the silicon component may be, for example, various silicone-modified resins such as epoxy resins, polyester resins, and phenolic resins, and sol-gel materials.
  • Metal salts made of formic acid, acetic acid, oxalic acid, and other organic acids may also be used.
  • An example of this type of metal salt is anhydrous copper formate.
  • the electronic component 10 may be provided with a glass film.
  • the glass film may be formed so as to cover a partial area of the outer surface 21 of the element body 20. In other words, even if there is a glass film covering the element body 20, it is sufficient that the electrical connection between the first internal electrode 41 and the first external electrode 61, and the electrical connection between the second internal electrode 42 and the second external electrode 62 are ensured.
  • An electronic component comprising: an element body; and an external electrode covering a portion of an outer surface of the element body and containing no silver components, wherein the external electrode has a base electrode covering the outer surface of the element body, the base electrode containing copper particles and a synthetic resin, wherein when the base electrode is divided into a first portion located on the element body side and a second portion located on the opposite side of the element body, the average particle size of the copper particles in the second portion is larger than the average particle size of the copper particles in the first portion.
  • the external electrode further comprises a metal layer covering the outer surface of the base electrode, and a mixed layer located between the metal layer and the base electrode, the mixed layer containing a chemical component not contained in the base electrode and contained in the metal layer, and containing a chemical component not contained in the metal layer and contained in the base electrode.

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  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013069713A (ja) * 2011-09-20 2013-04-18 Tdk Corp チップ型電子部品及びチップ型電子部品の製造方法
JP2014039000A (ja) * 2012-08-10 2014-02-27 Samsung Electro-Mechanics Co Ltd 積層セラミックキャパシタ及びその製造方法。
US20150090483A1 (en) * 2013-09-30 2015-04-02 Samsung Electro-Mechanics Co., Ltd. Multilayer ceramic capacitor, manufacturing method thereof, and board having the same mounted thereon
KR20190004631A (ko) * 2017-07-04 2019-01-14 삼성전기주식회사 적층 세라믹 커패시터
US20200185153A1 (en) * 2018-12-11 2020-06-11 Samsung Electro-Mechanics Co., Ltd. Capacitor component
JP2021174956A (ja) * 2020-04-30 2021-11-01 株式会社村田製作所 積層セラミックコンデンサ

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013069713A (ja) * 2011-09-20 2013-04-18 Tdk Corp チップ型電子部品及びチップ型電子部品の製造方法
JP2014039000A (ja) * 2012-08-10 2014-02-27 Samsung Electro-Mechanics Co Ltd 積層セラミックキャパシタ及びその製造方法。
US20150090483A1 (en) * 2013-09-30 2015-04-02 Samsung Electro-Mechanics Co., Ltd. Multilayer ceramic capacitor, manufacturing method thereof, and board having the same mounted thereon
KR20190004631A (ko) * 2017-07-04 2019-01-14 삼성전기주식회사 적층 세라믹 커패시터
US20200185153A1 (en) * 2018-12-11 2020-06-11 Samsung Electro-Mechanics Co., Ltd. Capacitor component
JP2021174956A (ja) * 2020-04-30 2021-11-01 株式会社村田製作所 積層セラミックコンデンサ

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