WO2023228888A1 - 回路部品 - Google Patents

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Publication number
WO2023228888A1
WO2023228888A1 PCT/JP2023/018838 JP2023018838W WO2023228888A1 WO 2023228888 A1 WO2023228888 A1 WO 2023228888A1 JP 2023018838 W JP2023018838 W JP 2023018838W WO 2023228888 A1 WO2023228888 A1 WO 2023228888A1
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WO
WIPO (PCT)
Prior art keywords
conductor layer
silica particles
conductor
crystallites
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/018838
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English (en)
French (fr)
Japanese (ja)
Inventor
裕明 佐野
登志文 東
晃 井本
貴史 山口
泉太郎 山元
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Kyocera Corp
Original Assignee
Kyocera Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kyocera Corp filed Critical Kyocera Corp
Priority to EP23811760.0A priority Critical patent/EP4535931A1/en
Priority to JP2024523093A priority patent/JPWO2023228888A1/ja
Priority to US18/867,233 priority patent/US20250338399A1/en
Priority to CN202380039927.3A priority patent/CN119174287A/zh
Publication of WO2023228888A1 publication Critical patent/WO2023228888A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0242—Shape of an individual particle
    • H05K2201/0257—Nanoparticles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0263—Details about a collection of particles
    • H05K2201/0266—Size distribution
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods
    • H05K3/1291—Firing or sintering at relative high temperatures for patterns on inorganic boards, e.g. co-firing of circuits on green ceramic sheets
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
    • H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
    • H05K3/4629—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials laminating inorganic sheets comprising printed circuits, e.g. green ceramic sheets

Definitions

  • the disclosed embodiments relate to circuit components.
  • wiring boards that have an insulating layer mainly composed of ceramics and a conductor layer mainly composed of metal.
  • Such a wiring board can be obtained, for example, by simultaneously firing a conductive material made of copper powder to which a metal oxide is added and glass ceramics as an insulating layer material (for example, see Patent Document 1).
  • the circuit component of the present disclosure includes an insulating layer made of ceramic, and a conductor layer extending inside the insulating layer in at least one of a planar direction and a direction intersecting the planar direction.
  • the conductor layer has a metal phase and silica particles, and the silica particles are surrounded by the metal phase.
  • FIG. 1 is an enlarged sectional view showing an example of the configuration of a wiring board according to an embodiment.
  • FIG. 2 is an enlarged view of area A shown in FIG.
  • FIG. 3 is a diagram showing a SEM observation photograph of the conductor layer of Sample 1.
  • FIG. 4 is a diagram showing an EPMA spectrum at measurement point 1 shown in FIG.
  • FIG. 5 is a diagram showing an EPMA spectrum at measurement point 2 shown in FIG.
  • circuit components include wiring boards, electronic components, and fuel cells. It goes without saying that the present disclosure can also be applied to filter elements, inductors, piezoelectric elements, etc., as long as an insulating layer and a conductive layer are combined and exhibit electrical characteristics.
  • wiring boards that have an insulating layer mainly composed of ceramics and a conductor layer mainly composed of metal.
  • Such a wiring board is obtained, for example, by simultaneously firing a conductive material made of copper powder to which a metal oxide is added and glass ceramics as an insulating layer material.
  • FIG. 1 is an enlarged sectional view showing an example of the wiring board 1 according to the embodiment
  • FIG. 2 is an enlarged view of area A shown in FIG.
  • the wiring board 1 according to the embodiment includes an insulating layer 10 and a conductor layer 20.
  • the insulating layer 10 can be made of, for example, a glass ceramic sintered body.
  • the glass ceramic sintered body may contain ceramics such as aluminum oxide, aluminum nitride, silicon carbide, silicon nitride, or mullite as a filler.
  • the insulating layer 10 may be made of glass ceramics, for example.
  • the wiring board 1 can be manufactured by simultaneously firing the green sheet, which is the raw material for the insulating layer 10, and the conductive paste, which is the raw material for the conductor layer 20. Therefore, according to the embodiment, the manufacturing cost of the wiring board 1 can be reduced.
  • the insulating layer 10 may include a first layer 11 and a second layer 12 facing each other with the conductor layer 20 in between.
  • the first layer 11 and the second layer 12 are located, for example, so as to sandwich both sides of the conductor layer 20 in the thickness direction.
  • the conductor layer 20 is electrically conductive and extends in the planar direction (lateral direction in FIG. 1) inside the insulating layer 10.
  • the conductor layer 20 is arranged, for example, between the first layer 11 and the second layer 12 in a predetermined pattern shape. Note that in the present disclosure, the conductor layer 20 may be exposed and located on the surface of the wiring board 1.
  • the conductor layer 20 has a metal phase and silica particles 22 (see FIG. 3). Moreover, such a metal phase includes a plurality of crystallites 21, as shown in FIG.
  • the crystallite 21 is made of a metal material such as copper, silver, palladium, gold, platinum-tungsten, molybdenum, or manganese, or an alloy material or mixed material containing these metal materials as main components.
  • the silica particles 22 may be surrounded by a metal phase (i.e., crystallites 21). This allows electricity to easily flow through the metal phase in the conductor layer 20, so that the electrical resistance of the conductor layer 20 can be reduced.
  • a metal phase i.e., crystallites 21
  • the silica particles 22 are preferably spherical.
  • the cross section of the silica particles 22 obtained by cutting or polishing the circuit board or the conductor layer 20 is preferably circular.
  • the conductor layer 20 is preferably in uniform contact with the entire periphery of the silica particles 22.
  • uniform means that when the composition of each of the silica particles 22 and the conductor layer 20 is analyzed from the center of the silica particle 22 to the conductor layer 20, each region of the silica particle 22 and the conductor layer 20 is This means that there is no change in the concentration of the main components of
  • each region is the range (width) from the center to the outer periphery of the silica particle 22.
  • the width on the conductor layer 20 side corresponds to the range (width) of the silica particles 22 described above.
  • the conductor layer 20 may have a width of 10 or less, where 1 is the range from the center to the outer periphery of the silica particles 22.
  • an analyzer EMA: Electron Probe Micro Analyzer
  • the material of the conductor layer for example, Cu
  • the components of the silica particles 22 can be measured from the conductor layer 20 to the center of the silica particles 22.
  • elemental mapping of Si was carried out, the count of Cu was not observed on the silica particle 22 side except for noise at the interface between the conductor layer 20 and the silica particle 22, and on the contrary, the count of Si was This refers to a state that is not observed on the conductor layer 20 side except for noise.
  • the silica particles 22 may be located at the interface between the conductor layer 20 and the insulating layer 10.
  • silica may exist in the form of particles on the surface of the conductor layer 20.
  • the surface of the conductor layer 20 refers to the vicinity of the interface between the insulating layer 10 and the conductor layer 20 when the conductor layer 20 is formed on the surface of the insulating layer 10.
  • This "near the interface” includes a small width range from the surface of the conductor layer 20 to the inside of the conductor layer 20.
  • This "slight width” is, for example, a range within 1 ( ⁇ m) from the surface of the conductor layer 20.
  • the presence of nano-sized silica particles 22 on the surface of the conductor layer 20 can improve the adhesion between the conductor layer 20 and the insulating layer 10.
  • the silica particles 22 may be present over the entire surface of the conductor layer 20 facing the insulating layer 10, or may be present only on a part of the surface of the conductor layer 20. When a plurality of silica particles 22 are present on the surface of the conductor layer 20, these silica particles 22 may be isolated from each other.
  • the shrinkage behavior of the metal material (for example, copper) used during firing is similar to the shrinkage behavior of the silica particles 22.
  • the reason why the shrinkage behavior of the metal material used for the conductor layer 20 during firing and the shrinkage behavior of the silica particles 22 are similar is considered to be that the size of the silica particles 22 is minute (nano size). .
  • silica particles larger than nano-sized are used, the particle size distribution will expand based on the size, and the heat capacity will increase due to the size. These factors become factors that change the sintering behavior and adhesion.
  • the temperature range in which the glass powder reaches a molten state is different from that of the nano-sized silica particles 22. It is wider than in the case of silica particles 22.
  • the melting temperature of glass powder may start at a lower temperature than that of nano-sized silica particles 22.
  • glass powder often has a wide particle size distribution. When glass powder having these properties is used, the glass powder tends to aggregate or move during sintering within the printed pattern that becomes the conductor layer 20.
  • nano-sized silica particles 22 when they have a single composition, the temperature range in which they reach a molten state is narrower than when using glass powder. As a result, the conductor layer 20 becomes dense, and gently shaped recesses are likely to be formed on the surface along the insulating layer 10.
  • the wiring board 1 is fired at a temperature that is below the melting point of the main component metal and silica particles 22 contained in the conductor layer 20 and higher than the partial melting temperature of the insulating layer 10.
  • the melting temperature of composite oxide glass powder varies depending on the composition, and the range from the melting start temperature to the temperature at which it completely melts is wide. That is, the composite oxide glass powder may partially melt at a temperature lower than the firing temperature of the wiring board 1 (700° C. or higher and 1000° C. or lower).
  • the firing temperature is not lower than the melting point of the glass powder by 500°C or more; It easily diffuses and reacts easily with the insulating layer 10.
  • the temperature, melting point, and softening point at which each material of the insulating layer 10 and the conductive layer 20 starts to melt is determined by, for example, suggestive thermal analysis.
  • the content rate of the silica particles 22 in the conductor layer 20 may be 0.3 to 2.5 in terms of mass ratio when the metal phase is taken as 100. Thereby, the adhesion between the conductor layer 20 and the insulating layer 10 can be improved.
  • a specific range (for example, region A) of the conductor layer 20 is specified in a cross-sectional view, the straight line length in the plane direction (horizontal direction in FIG. 2) is set as L0, and the length of the outline 20a of the conductor layer 20 is
  • L1 is the length (that is, the length of the interface between the conductor layer 20 and the insulating layer 10)
  • L1/L0 may be in the range of 1.05 to 1.15.
  • the specific range is a range in which the width of the conductor layer 20 in the longitudinal direction is greater than or equal to 10 ( ⁇ m) and less than or equal to 100 ( ⁇ m).
  • the width in the longitudinal direction in this specific range can be selected from a range of 10 ( ⁇ m) or more and 100 ( ⁇ m) or less.
  • Such an arbitrary width is determined in consideration of the thickness of the conductor layer 20, the size of the crystallites 21 contained in the conductor layer 20, and the like.
  • the specific range may be a range in which one conductor layer 20 is sandwiched between upper and lower insulating layers 10.
  • the specific range multiple locations in the photographed photograph may be specified.
  • the interfacial conductivity of the conductor layer 20 can be increased.
  • the particle size of the silica particles 22 according to the embodiment is preferably 1 (nm) to 50 (nm).
  • the particle size refers to the diameter.
  • the diameter refers to the maximum diameter obtained when observing the silica particles 22.
  • the silica particles 22 preferably have an average particle diameter of 20 (nm).
  • the conductor layer 20 may include silica particles 22 having a particle size of 10 (nm) to 40 (nm) in an integrated amount ratio of 70 (%) or more.
  • the particle size refers to the diameter of the portion of the silica particle that exhibits the maximum length when the cross section of the conductor layer 20 is observed.
  • the aspect ratio (major axis/breadth axis) of the silica particles 22 may be 1.5 or less. Note that the major axis is the longest part of the silica particle 22, and the minor axis is the shortest part in the direction perpendicular to the major axis.
  • the conductor layer 20 may have a microstructure formed by fine copper crystallites 21.
  • the plurality of crystallites 21 include those having a polygonal shape including linear sides, and are in contact with the sides as grain boundaries.
  • the longest diameter of the crystallite 21 is preferably greater than or equal to 1 ( ⁇ m) and less than or equal to 10 ( ⁇ m).
  • the plurality of crystallites 21 preferably have a number ratio of 70 (%) or more of crystallites having two or more sides.
  • the area ratio of the silica particles 22 in the conductor layer 20 may be 0.006 (%) to 0.069 (%). Thereby, the interfacial conductivity of the conductor layer 20 can be increased. Note that how to determine the area ratio of the silica particles 22 in the conductor layer 20 will be described later.
  • the crystallite 21 may be composed of copper as a main component, and the copper content in the conductor layer 20 may be 80 (wt%) to 99 (wt%). Thereby, the interfacial conductivity of the conductor layer 20 can be further increased.
  • the crystallites 21 may have a polygonal shape. This makes it possible to reduce the decrease in the interfacial conductivity in a high frequency region (for example, 1 (GHz) to 49 (GHz)), thereby increasing the interfacial conductivity of the conductor layer 20 in the high frequency region.
  • a high frequency region for example, 1 (GHz) to 49 (GHz)
  • the bond between adjacent crystallites 21 is strong and the crystallites 21 are dense, it is possible to reduce variations in electrical resistance when the conductor layer 20 is divided in the length direction. .
  • the present disclosure can also be applied to a wiring board using silver for the conductor layer.
  • the structure shown in FIG. 1 can also be applied to this wiring board. That is, the conductor layer is placed inside the insulating layer.
  • the material of the conductor layer may be silver (Ag).
  • the silver conductor layer is a sintered metal having multiple crystallites.
  • the silver conductor layer preferably contains silica particles in a sintered metal body.
  • this conductor layer is preferably a composite metal film obtained by sintering silver powder containing silica particles.
  • the size of the silica particles is preferably about the same size as the crystallites or smaller. Specifically, the silica particles preferably have an average particle diameter of 20 (nm). Further, the conductor layer may contain silica particles having a particle size of 10 (nm) to 40 (nm) in a cumulative amount of 70 (%) or more. In this case, the particle size refers to the diameter of the portion of the silica particle that exhibits the maximum length when the cross section of the conductor layer is observed.
  • the size refers to the diameter of the part of the crystallite that exhibits the maximum length when the cross section of the conductor layer is observed.
  • the conductor layer is a composite metal film obtained by sintering silver powder containing silica particles
  • the silver metal phase has a crystal structure in which a plurality of crystallites are in contact with each other on their sides.
  • silica particles are included in the silver powder during firing, silver grain growth is suppressed by the presence of the silica particles.
  • metal powder grows three-dimensionally, but when silica particles are present adjacent to silver powder, the grains grow in the direction of the silica particles on the surface of the aggregate of multiple silver powders. grain growth is suppressed. In a metal sintered body formed from silver powder, the grain growth direction is restricted by silica particles.
  • the conductor layer which is a sintered body of silver in which silica particles are present in the silver powder, tends to have a crystal structure in which a plurality of crystallites are in contact with each other on their sides.
  • the area ratio of the crystal structure in which a plurality of crystallites contained in the conductor layer are in contact with each other on their sides is preferably 70 (%) or more per unit area.
  • the shape of the plurality of crystallites existing adjacent to each other in the conductor layer is polygonal.
  • the portions where the polygonal crystallites are in contact with each other have straight sides.
  • the straight edges are grain boundaries.
  • Polygonal crystallites are in contact with each other via linear grain boundaries.
  • the conductor layer has a low resistance value. Furthermore, the interfacial conductivity in a high frequency band is high. Moreover, the void ratio in the conductor layer becomes low. In this way, the conductor resistance (interfacial conductivity) of the conductor layer and the coverage of the conductor layer on the surface of the insulating layer can be increased.
  • the interfacial conductivity was 80 (%).
  • Ta the firing in this case was performed in an air atmosphere.
  • the average particle size of the silver powder was 2 ( ⁇ m).
  • the average particle diameter of the silica particles was 20 (nm).
  • the conductor layer of the fabricated wiring board had a crystalline structure in which multiple crystallites were in contact with each other on their sides.
  • the area ratio of the crystal structure in which a plurality of crystallites contained in the conductor layer were in contact with each other side by side was about 75 (%) per unit area. In this case, most of the crystallites existing adjacent to each other in the conductor layer had a polygonal shape.
  • the portion where the polygonal crystallites were in contact with each other had straight sides.
  • the straight edges were grain boundaries.
  • the polygonal crystallites were in contact with each other through linear grain boundaries.
  • the area ratio of silica particles in the conductor layer was comparable to that of Sample 2 in Table 1 below.
  • This electronic component also has a conductor layer inside the insulating layer.
  • the conductor layer may be sandwiched between the first layer and the second layer, as in the wiring board 1 described above.
  • the conductor layer may be arranged on both sides of the insulating layer.
  • the material of the conductor layer is preferably nickel.
  • the material of the insulating layer is preferably a ceramic material exhibiting dielectric properties. Ceramic materials exhibiting dielectric properties may be referred to as dielectric ceramics.
  • dielectric ceramics examples include ceramic materials containing barium titanate as a main component.
  • main component refers to a case where barium titanate is contained in the dielectric ceramic at 80 (mol %) or more.
  • Dielectric ceramics are applied, for example, to dielectric layers of multilayer ceramic capacitors.
  • the nickel conductor layer is a sintered metal having multiple crystallites.
  • the nickel conductor layer preferably contains silica particles in the sintered body.
  • this conductor layer is preferably a composite metal film made by sintering nickel powder containing silica particles.
  • the size of the silica particles is preferably about the same size as the crystallites or smaller.
  • the size refers to the diameter of the part of the crystallite that exhibits the maximum length when the cross section of the conductor layer is observed.
  • the silica particles preferably have an average particle size of 20 (nm).
  • the conductor layer may contain silica particles having a particle size of 10 (nm) to 40 (nm) in a cumulative amount of 70 (%) or more.
  • the particle size refers to the diameter of the portion of the silica particle that exhibits the maximum length when the cross section of the conductor layer is observed.
  • the conductor layer is a composite metal film obtained by sintering nickel powder containing silica particles
  • the nickel metal phase has a crystal structure in which a plurality of crystallites are in contact with each other on their sides.
  • One reason for this is thought to be that when firing is performed with silica particles included in the nickel powder, the grain growth of nickel is suppressed by the presence of the silica particles.
  • metal powder grows three-dimensionally, but when there are silica particles adjacent to nickel powder, the surface of the aggregate of multiple nickel powders grows in the direction where the silica particles exist. Grain growth is suppressed. In a metal sintered body formed from nickel powder, the grain growth direction is restricted by silica particles.
  • the conductor layer which is a sintered body of nickel in which silica particles are present in the nickel powder, tends to have a crystal structure in which a plurality of crystallites are in contact with each other on their sides.
  • the area ratio of the crystal structure in which a plurality of crystallites contained in the conductor layer are in contact with each other on their sides is preferably 70 (%) or more per unit area.
  • the shape of the plurality of crystallites existing adjacent to each other in the conductor layer is polygonal.
  • the portions where the polygonal crystallites are in contact with each other have straight sides.
  • the straight edges are grain boundaries.
  • Polygonal crystallites are in contact with each other via linear grain boundaries. Thereby, the conductor layer has a low resistance value.
  • the conductor layer has a low void ratio. In this way, it is possible to increase the conductor resistance of the conductor layer and the coverage on the surface of the dielectric ceramic (also referred to as a dielectric layer). As a result, it becomes possible to increase the capacitance per unit volume of the multilayer ceramic capacitor.
  • the capacitance of a sample (sample A) in which silica particles are not included in the nickel conductor layer is set to 1.
  • the capacitance of the sample (sample B) in which silica particles are included in the nickel conductor layer is 1.1 times or more.
  • the capacitance of sample B was 1.2 times the capacitance of sample A.
  • the composition of the dielectric layer when forming samples A and B was 100 (mol parts) of barium titanate powder, 1 (mol part) of magnesium oxide powder, and 1.5 (mol parts) of rare earth element (yttrium oxide). 1 (mol part) of manganese oxide (MnO) is added.
  • the conductor layer was produced using 100 (parts by mass) of nickel powder to which 1 (part by mass) of silica particles was added.
  • the average particle size of the nickel powder was 0.1 ( ⁇ m).
  • the average particle diameter of the silica particles was 20 (nm).
  • the capacitor was created by printing a nickel conductive paste on both sides of a single plate-shaped molded body with a dielectric layer of 10 (mm) in diameter and 1 (mm) in thickness, and firing it.
  • the firing conditions were such that the maximum temperature was 1200 (°C) and the holding time at the maximum temperature was 2 (hours).
  • An LCR meter (4274A manufactured by HP) was used to measure the capacitance of the prepared samples A and B.
  • the measurement frequency was 1 (KHz) and the measurement voltage was 0.5 (V).
  • the conductor layer of the fabricated capacitor had a crystalline structure in which multiple crystallites were in contact with each other on their sides.
  • the area ratio of the crystal structure in which a plurality of crystallites contained in the conductor layer were in contact with each other side by side was about 75 (%) per unit area. In this case, most of the crystallites existing adjacent to each other in the conductor layer had a polygonal shape.
  • the portion where the polygonal crystallites were in contact with each other had straight sides.
  • the straight edges were grain boundaries.
  • the polygonal crystallites were in contact with each other through linear grain boundaries.
  • the area ratio of silica particles in the conductor layer was comparable to that of Sample 2 in Table 1 below.
  • a fuel cell has a fuel electrode and a support.
  • the fuel electrode includes a solid electrolyte material and nickel.
  • the main component of the fuel electrode material is zirconia.
  • the material for the conductor is preferably nickel.
  • the nickel conductor preferably contains silica particles in its sintered body.
  • this conductor is preferably a composite metal made by sintering nickel powder containing silica particles.
  • the size of the silica particles is preferably about the same size as or smaller than the crystallites constituting the nickel conductor after sintering.
  • the size refers to the diameter of the point of maximum length in the crystallite when observing the cross section of the conductor.
  • the silica particles preferably have an average particle diameter of 20 (nm).
  • the conductor may contain silica particles having a particle size of 10 (nm) to 40 (nm) in a cumulative amount of 70 (%) or more.
  • the particle size refers to the diameter of the portion of the silica particle that exhibits the maximum length when the cross section of the conductor is observed.
  • the conductor is a composite metal film made by sintering nickel powder containing silica particles
  • the nickel metal phase has a crystal structure in which a plurality of crystallites are in contact with each other on their sides.
  • One reason for this is thought to be that when firing is performed with silica particles included in the nickel powder, the grain growth of nickel is suppressed by the presence of the silica particles.
  • metal powder grows three-dimensionally, but when there are silica particles adjacent to nickel powder, the surface of the aggregate of multiple nickel powders grows in the direction where the silica particles exist. Grain growth is suppressed.
  • a conductor layer which is a sintered body of nickel in which silica particles are present in nickel powder, tends to have a crystal structure in which a plurality of crystallites are in contact with each other on their sides.
  • the area ratio of the crystal structure in which a plurality of crystallites contained in the conductor are in contact with each other on their sides is 70 (%) or more per unit area.
  • the shape of the plurality of crystallites existing adjacent to each other in the conductor is polygonal.
  • the portions where the polygonal crystallites are in contact with each other have straight sides.
  • the straight edges are grain boundaries.
  • Polygonal crystallites are in contact with each other via linear grain boundaries. As a result, the conductor has a low resistance value.
  • the conductor has a low void ratio. In this way, the conductor can reduce the conductor resistance and increase the coverage on the surface of the zirconia sintered body. As a result, it becomes possible to obtain a fuel cell with low conductor resistance.
  • Conductor resistance is a temperature above room temperature, and it also greatly contributes to a reduction in conductor resistance at temperatures below 1000 (°C), below 700 (°C), and below 500 (°C).
  • a sample in the form of a single plate was prepared.
  • Sample C was prepared by mixing 50 (parts by mass) of zirconia (stabilized zirconia with Y of 10 (mol%)) and 50 (parts by mass) of nickel powder to which no silica particles were added, and producing a molded body. , and was produced by firing.
  • Sample D was prepared by mixing 50 (parts by mass) of zirconia (stabilized zirconia with Y of 10 (mol%)) and 50 (parts by mass) of composite metal powder in which the surface of nickel powder was coated with silica particles, and forming a molded body. After manufacturing, firing was performed.
  • the molded body was in the shape of a disk with a diameter of 10 (mm) and a thickness of 1 (mm).
  • the zirconia powder used had an average particle size of 5 ( ⁇ m).
  • the nickel powder used had an average particle size of 3 ( ⁇ m).
  • the silica particles used had an average particle diameter of 20 (nm).
  • the amount of silica particles added was 1 (part by mass) per 100 (parts by mass) of nickel powder.
  • the firing was performed in an oxygen-containing atmosphere at a maximum temperature of 1300 (°C) and a holding time of 2 hours. After this, the resistance value of each of the prepared materials was measured. The measurements were performed with samples C and D heated to a temperature of 700 (°C).
  • a platinum wire was connected to samples C and D, so that the platinum wire was pulled out from the heating furnace in which samples C and D were held.
  • the platinum wire was connected to the terminal of a resistance measuring device placed in a room temperature environment.
  • the resistance value of the sample to which silica particles were added was 0.95 times or less the resistance value (resistance value at direct current) of the sample to which silica particles were not included (sample C). Specifically, the resistance value of sample D was 0.93 times the resistance value of sample C.
  • the cross section of the nickel conductor layer was observed using an electron microscope.
  • the conductor had a crystal structure in which multiple crystallites were in contact with each other. Most of the crystallites were polygonal in shape. The portions where the polygonal crystallites were in contact with each other had straight sides.
  • the straight edges were grain boundaries.
  • the polygonal crystallites were in contact with each other through linear grain boundaries.
  • the area ratio of silica particles in the conductor was comparable to that of Sample 2 in Table 1 below.
  • a mixture of 40 (wt%) alumina particles and 60 (wt%) borosilicate glass was prepared as a material for the insulating layer.
  • Such a mixture is a raw material for glass ceramics with a firing temperature of 900 (°C) to 1000 (°C).
  • copper powder purity 99.9 (wt%)
  • silica particles with an average particle size of 20 (nm) were prepared.
  • the cumulative amount of silica particles having a diameter of 10 (nm) to 40 (nm) was 75 (%).
  • the content of silica particles was 0.3 (parts by mass) with respect to 100 (parts by mass) of copper powder.
  • a mixed solvent of isobutyl methacrylate resin, butyl carbitol acetate, and dibutyl phthalate was used as the organic binder. Then, isobutyl methacrylate resin is added at a ratio of 5 (parts by mass) to 100 (parts by mass) of copper powder, and a mixed solvent of butyl carbitol acetate and dibutyl phthalate is further added to contain copper powder and silica particles. A conductive paste was prepared.
  • a conductive paste was printed on both surfaces of the produced green sheet in a predetermined area and fired.
  • the firing was performed in a reducing atmosphere using a hydrogen-nitrogen mixed gas at a maximum temperature of 930 (° C.) and a holding time of 2 (hours).
  • a plurality of green sheets were stacked to have a thickness of 500 ( ⁇ m). Thereby, wiring board 1 of sample 1 was obtained.
  • Example 6 The wiring board 1 of Sample 6 was obtained using the same method and conditions as Sample 1 described above except for the process of producing the conductor paste.
  • copper powder purity 99.9 (wt%)
  • borosilicate glass powder with an average particle size of 2 ( ⁇ m) were prepared as raw materials for the conductor layer.
  • the content of the glass powder was 1.0 (parts by mass) with respect to 100 (parts by mass) of the copper powder.
  • a mixed solvent of isobutyl methacrylate resin, butyl carbitol acetate, and dibutyl phthalate was used as the organic binder.
  • a conductor containing copper powder and glass powder by adding isobutyl methacrylate resin at a ratio of 5 (parts by mass) to 100 (parts by mass) of copper powder, and further adding a mixed solvent of butyl carbitol acetate and dibutyl phthalate.
  • a paste was prepared.
  • Wiring substrates 1 of Samples 7 and 8 were obtained using the same method and conditions as Sample 6 described above except for the content of borosilicate glass powder in the process of preparing the conductor paste.
  • the amount was set to 3.0 (parts by mass) and 5.0 (parts by mass), respectively, with respect to 100 (parts by mass) of copper powder.
  • FIG. 3 is a diagram showing a SEM observation photograph of the conductor layer 20 of Sample 1.
  • 4 is a diagram showing an EPMA spectrum at measurement point 1 shown in FIG. 3
  • FIG. 5 is a diagram showing an EPMA spectrum at measurement point 2 shown in FIG. 3.
  • silica particles 22 (Si peak was observed) were located between adjacent copper crystallites 21 (corresponding to measurement point 2 where no Si peak was observed). (corresponding to measurement point 1) was observed. In other words, in the embodiment, the silica particles 22 were observed to be surrounded by the metal phase (namely, the crystallites 21).
  • silica particles 22 were also observed to be located at the interface between the conductive layer 20 and the insulating layer 10.
  • point A and point B are attached to both ends of one outline 20a for the conductor layer 20 shown in the cross-sectional photograph, and a straight line is drawn between the points A and B.
  • the length of this straight line was defined as L0.
  • the length of the contour 20a from point A to point B was determined, and this length was defined as L1.
  • L1/L0 was determined as the ratio of both lengths.
  • the area ratio of the silica particles 22 in each of Samples 1 to 8 was measured. Specifically, first, a plurality of square ranges with a length of 1/10 to 1/2 of the thickness of the conductor layer 20 shown in the cross-sectional photograph were specified. For example, 8 to 10 such square ranges are specified so that they are arranged continuously in the direction in which the conductor layer 20 extends (planar direction).
  • the area of the metal portion (corresponding to the crystallites 21) in the area divided by the squares was set as A0. Further, the area of the black portion (corresponding to the silica particles 22) shown in FIG. 3 was defined as A1.
  • the ratio A1/A0 of both areas was taken as the area ratio of the silica particles 22 in one square area.
  • the average value of the area proportions of the silica particles 22 in a plurality of square areas was taken as the area proportion of the silica particles 22 of this sample.
  • the silica particles 22 were identified using EPMA.
  • the center of the position judged to be the silica component and the position judged to be the metal phase is the boundary between the silica particles 22 and the metal phase. And so.
  • interfacial conductivity of each of the wiring boards 1 of Samples 1 to 8 obtained above was measured.
  • the interfacial conductivity was measured by the dielectric cylindrical resonator method described below. Further, as a sample for measurement, one having a diameter of 50 (mm) and having a conductor layer 20 formed over almost the entire surface of both surfaces was used.
  • a method for measuring interfacial conductivity using the dielectric cylinder resonator method is to form the above-mentioned conductor inside on both end faces or one end face of a dielectric cylinder made of a dielectric material whose relative dielectric constant and dielectric loss are known. This method measures the conductivity at the interface between a conductor and an insulating layer, that is, at the conductor interface, by attaching insulating layers in a predetermined relationship to form a dielectric resonator.
  • the principle of this measurement method is that a conductor plate (usually the diameter of the dielectric cylinder
  • a conductor plate usually the diameter of the dielectric cylinder
  • conductor plates having a diameter D approximately three times as large as That is, this is due to the fact that it is distributed only on the opposing surfaces of the dielectric and the conductor.
  • a high frequency current flowing through a conductor in TEomn mode flows through the dielectric material in contact with the conductor and the dielectric cylinder.
  • the interfacial conductivity was measured at a frequency of 10 (GHz).
  • the sample for evaluation was cut at a position approximately 1/2 the length in one direction, and both the interface between the insulating layer 10 and the conductor layer 20 in the cross section was observed. . If a peeled portion was observed at even one location, it was determined that there was "peeling", and if no peeled portion was found at any interface, it was determined that there was "no peeling".
  • the state of "peeling” is defined as a case where the length of the region where the distance between the insulating layer 10 and the conductor layer 20 is 0.1 (mm) or more is 1 (mm) or more. .
  • a thermal shock resistance test was conducted by immersing the wiring boards 1 of Samples 1 to 8 obtained above in a heated solder bath for about 1 second.
  • cracks generated in the wiring board 1 were confirmed by observing a cross-sectionally polished sample of the wiring board 1 using a stereomicroscope. A sample with no visible cracks was evaluated as "A,” a sample with few cracks was evaluated as “B,” and a sample with many cracks was evaluated as "C.”
  • Table 1 shows the measurement results of the interfacial conductivity at (GHz), the evaluation results of the presence or absence of conductor peeling, and the test results of the thermal shock resistance test. Note that the measurement results of the interfacial conductivity at a frequency of 10 (GHz) are relative values when the interfacial conductivity at direct current is 100 (%).
  • the interfacial conductivity of the conductor layer 20 can be increased to 80 (%) or more.
  • the electrical resistance of the conductor layer 20 can be reduced by surrounding the silica particles 22 with the metal phase.
  • a conductive paste was prepared using a conductor paste in which the content of silica particles 22 was 0.3 (parts by mass) to 3.0 (parts by mass) with respect to 100 (parts by mass) of copper powder. According to Samples 1 to 5, it is found that the interfacial conductivity of the conductor layer 20 can be increased and the peeling of the conductor of the conductor layer 20 can be reduced.
  • samples 1 to 4 prepared using conductor pastes in which the content of silica particles 22 is 0.3 (parts by mass) to 2.5 (parts by mass) with respect to 100 (parts by mass) of copper powder. It can be seen that the interfacial conductivity of the conductor layer 20 can be made higher, conductor peeling of the conductor layer 20 can be reduced, and good thermal shock resistance can be obtained.
  • the interfacial conductivity of the conductor layer 20 can be made higher, conductor peeling of the conductor layer 20 can be reduced, and a good It can be seen that thermal shock resistance can be obtained.
  • the interfacial conductivity of the conductor layer 20 can be further increased. Furthermore, it can be seen that by setting the value of L1/L0 in the conductor layer 20 in the range of 1.05 to 1.09, the interfacial conductivity of the conductor layer 20 can be further increased.
  • the value of L1/L0 in the conductor layer ends up being 2 or more. Further, in this printed circuit board, since the contour of the conductor layer has large irregularities, the interfacial conductivity of the conductor layer decreases.
  • the interfacial conductivity of the conductor layer 20 can be increased. , it can be seen that conductor peeling of the conductor layer 20 can be reduced.
  • the interfacial conductivity of the conductor layer 20 can be made higher, and the conductor of the conductor layer 20 can be It can be seen that peeling can be reduced and good thermal shock resistance can be obtained.
  • the interfacial conductivity of the conductor layer 20 can be made higher, and the It can be seen that the interfacial conductivity can be further increased.
  • the interfacial conductivity of the conductor layer 20 can be further increased by setting the area ratio of the silica particles 22 in the conductor layer 20 to a range of 0.006 (%) to 0.026 (%).
  • fine ceramic powder other than silica for example, fine alumina powder, etc.
  • fine alumina powder for example, fine alumina powder, etc.
  • Wiring board (an example of circuit components) 10 insulating layer 20 conductor layer 20a outline 21 crystallite 22 silica particle

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
PCT/JP2023/018838 2022-05-27 2023-05-19 回路部品 Ceased WO2023228888A1 (ja)

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EP23811760.0A EP4535931A1 (en) 2022-05-27 2023-05-19 Circuit component
JP2024523093A JPWO2023228888A1 (https=) 2022-05-27 2023-05-19
US18/867,233 US20250338399A1 (en) 2022-05-27 2023-05-19 Circuit component
CN202380039927.3A CN119174287A (zh) 2022-05-27 2023-05-19 电路部件

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06305770A (ja) * 1993-04-22 1994-11-01 Nec Corp 多層ガラスセラミック基板とその製造方法
JP2001044633A (ja) * 1999-07-30 2001-02-16 Hitachi Ltd セラミック回路基板
JP2003277852A (ja) 2002-03-25 2003-10-02 Kyocera Corp 銅メタライズ組成物およびセラミック配線基板
JP2004134378A (ja) * 2002-07-17 2004-04-30 Ngk Spark Plug Co Ltd 銅ペーストとそれを用いた配線基板
JP2007081320A (ja) * 2005-09-16 2007-03-29 Tdk Corp 多層セラミックス基板

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06305770A (ja) * 1993-04-22 1994-11-01 Nec Corp 多層ガラスセラミック基板とその製造方法
JP2001044633A (ja) * 1999-07-30 2001-02-16 Hitachi Ltd セラミック回路基板
JP2003277852A (ja) 2002-03-25 2003-10-02 Kyocera Corp 銅メタライズ組成物およびセラミック配線基板
JP2004134378A (ja) * 2002-07-17 2004-04-30 Ngk Spark Plug Co Ltd 銅ペーストとそれを用いた配線基板
JP2007081320A (ja) * 2005-09-16 2007-03-29 Tdk Corp 多層セラミックス基板

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CN119174287A (zh) 2024-12-20

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