WO2023189993A1 - 銀微粒子 - Google Patents

銀微粒子 Download PDF

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Publication number
WO2023189993A1
WO2023189993A1 PCT/JP2023/011397 JP2023011397W WO2023189993A1 WO 2023189993 A1 WO2023189993 A1 WO 2023189993A1 JP 2023011397 W JP2023011397 W JP 2023011397W WO 2023189993 A1 WO2023189993 A1 WO 2023189993A1
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WO
WIPO (PCT)
Prior art keywords
silver
particles
gas
silver particles
fine particles
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/JP2023/011397
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English (en)
French (fr)
Japanese (ja)
Inventor
志織 末安
周 渡邉
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Nisshin Engineering Co Ltd
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Nisshin Engineering Co Ltd
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Application filed by Nisshin Engineering Co Ltd filed Critical Nisshin Engineering Co Ltd
Priority to KR1020247032225A priority Critical patent/KR20240168337A/ko
Priority to JP2024512250A priority patent/JPWO2023189993A1/ja
Priority to US18/853,040 priority patent/US20250249503A1/en
Priority to CN202380029481.6A priority patent/CN119300931A/zh
Publication of WO2023189993A1 publication Critical patent/WO2023189993A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/12—Making metallic powder or suspensions thereof using physical processes starting from gaseous material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0466—Alloys based on noble metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
    • B22F2301/255—Silver or gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/05—Submicron size particles
    • B22F2304/056—Particle size above 100 nm up to 300 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/05—Submicron size particles
    • B22F2304/058—Particle size above 300 nm up to 1 micrometer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/062—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts
    • B22F7/064—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts using an intermediate powder layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder

Definitions

  • the present invention relates to silver particles used for bonding semiconductor elements, high frequency devices, light emitting diodes, semiconductor lasers, etc. and substrates, etc.
  • power semiconductor devices using wide bandgap semiconductors such as silicon carbide (SiC), gallium nitride (GaN), gallium oxide, or diamond are being developed.
  • Power semiconductor devices have lower on-resistance than semiconductor devices using Si or GaAs, can be switched at high speed, and can be made smaller.
  • power semiconductor elements have high heat resistance and can operate at high temperatures of 250 to 300°C.
  • Solder has conventionally been used to bond semiconductor elements and substrates.
  • the operating temperature of power semiconductor devices is higher than that of conventional semiconductor devices using Si or GaAs, and when bonding using solder, it is necessary to use the device at a temperature at which the solder does not melt.
  • solder is used for bonding, there are restrictions on the use of power semiconductor devices. In this way, bonding materials are also required to be usable at high temperatures.
  • Patent Document 1 includes low-temperature sinterable silver particles and a thermosetting binder, and the thermosetting binder is (B1) phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydro At least one epoxy resin selected from the group consisting of phthalic acid diglycidyl esters and their C1 to C4 alkyl substituted products, and (B2) the group consisting of cationic polymerization initiators, amine curing agents, and acid anhydride curing agents.
  • a thermally conductive paste is described in which the thermosetting binder is comprised of at least one type of curing agent selected from the above, and the thermosetting binder is contained in an amount of 2 to 7 parts by mass based on 100 parts by mass of silver particles.
  • thermosetting binder When a thermosetting binder is contained as in Patent Document 1, the volume shrinkage rate is small.
  • a bonding material with a small volume shrinkage rate is used as in Patent Document 1 mentioned above.
  • the substrate cannot be uniformly bonded to the plurality of semiconductor elements, and a sufficient bonding state cannot be maintained.
  • the bonding material needs to have a large volumetric shrinkage. Further, it is preferable that the bonding material has excellent electrical conductivity.
  • An object of the present invention is to provide fine silver particles that have a large volumetric shrinkage and are highly conductive.
  • one embodiment of the present invention has a particle size of 0.1 ⁇ m or more and 1 ⁇ m or less as measured by the BET method, and is calcined in the form of pellets at a temperature of 100° C. for 1 hour in a nitrogen atmosphere.
  • the present invention provides silver particles having a subsequent volume resistivity of 15 ⁇ cm or less and a volume shrinkage rate of 5% or more.
  • the particle size measured by the BET method is 0.1 ⁇ m or more and 1 ⁇ m or less, the volume resistivity after firing the pellet in a nitrogen atmosphere at a temperature of 150°C for 1 hour is 10 ⁇ cm or less, and the volume shrinkage rate is
  • the present invention provides silver fine particles having a content of 10% or more.
  • the particle size measured by the BET method is 0.1 ⁇ m or more and 1 ⁇ m or less, the volume resistivity after firing in pellet form at 150°C for 1 hour in the air is 10 ⁇ cm or less, and the volume shrinkage rate is 5 % or more.
  • the surface is coated with an aliphatic amine.
  • the aliphatic amine preferably has 10 to 18 carbon atoms.
  • FIG. 1 is a schematic diagram showing an example of a usage form of silver fine particles of the present invention. It is a schematic diagram which shows another example of the utilization form of the silver fine particle of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example of the manufacturing apparatus of silver fine particles of this invention.
  • FIG. 2 is a schematic diagram showing a SEM image of silver fine particles of Example 1 of the present invention.
  • FIG. 2 is a schematic diagram showing a SEM image of silver fine particles of Example 2 of the present invention.
  • the silver fine particles have a particle size of 0.1 ⁇ m or more and 1 ⁇ m or less as measured by the BET method, a volume resistivity of 15 ⁇ cm or less after being fired in a pellet form at a temperature of 100° C. for 1 hour in a nitrogen atmosphere, and The volumetric shrinkage rate is 5% or more.
  • the nitrogen atmosphere refers to an atmosphere in which nitrogen gas with a purity of 99.99 (nitrogen 99.99 volume %) is constantly flowing, and an atmosphere in which the oxygen concentration is 100 volume ppm or less.
  • the oxygen concentration can be set to 100 volume ppm or less, and a gas such as a rare gas, for example, a rare gas, which does not react with silver, may be mixed with nitrogen.
  • the oxygen concentration can be measured using, for example, a low concentration oxygen analyzer PS-820-L manufactured by Iijima Electronics Co., Ltd.
  • the particle size of the silver fine particles is preferably 100 to 400 nm, and 300 to 400 nm, because of the ease of handling during dispersion and the small volume shrinkage after firing in a nitrogen atmosphere at 100°C for 1 hour in pellet form. 400 nm is more preferred.
  • the volume resistivity value is 15 ⁇ cm or less, preferably 10 ⁇ cm or less, and more preferably 8 ⁇ cm or less. Further, the lower limit of the volume resistance value is 1.47 ⁇ cm. Further, the volume shrinkage rate is 5% or more, preferably 6% or more. Further, the upper limit of the volume shrinkage rate is 40%.
  • the particle size of silver fine particles measured by the BET method is the average particle size measured using the BET method. In the BET method, it is calculated from the specific surface area assuming that the particles are spherical.
  • the silver fine particles are not dispersed in a solvent or the like, but exist alone without a solvent or the like. Therefore, when using fine silver particles, a fired body can be obtained using only the fine silver particles. Further, when silver particles are used in combination with a solvent, the combination of silver particles and solvent is not particularly limited, and there is a high degree of freedom in selecting the solvent.
  • volume resistivity value is a value obtained by measuring with a four-probe method using pellets.
  • Loresta EP MCP-T360
  • Mitsubishi Chemical Corporation is used as the measuring device.
  • volume shrinkage rate was determined by holding silver fine particles for 10 seconds at a pressure of 127 MPa using a press machine as described above to produce a cylindrical pellet, and measuring the thickness and diameter of the cylindrical pellet with a caliper. This is a value calculated from the volume of pellets before and after firing.
  • the silver fine particles have a particle size of 0.1 ⁇ m or more and 1 ⁇ m or less as measured by the BET method, a volume resistivity of 15 ⁇ cm or less after being fired in a pellet form at a temperature of 100° C. for 1 hour in a nitrogen atmosphere, and When the volumetric shrinkage rate is 5% or more, the volumetric shrinkage is large and the conductivity is high. Furthermore, silver particles have a higher melting point than solder and the like, and have excellent heat resistance. Therefore, when silver fine particles are used as a bonding material, it is possible to achieve excellent electrical conductivity while satisfying heat resistance.
  • the silver fine particles have a particle size of 0.1 ⁇ m or more and 1 ⁇ m or less as measured by the BET method, and have a volume resistivity of 10 ⁇ cm or less after being fired in a pellet form at a temperature of 150° C. for 1 hour in a nitrogen atmosphere, and The volumetric shrinkage rate is 10% or more.
  • the particle size of the silver fine particles is preferably 100 to 600 nm, and 300 to 600 nm, because of the ease of handling during dispersion and the small volume shrinkage after firing in a nitrogen atmosphere at a temperature of 150°C for 1 hour in pellet form.
  • the wavelength is more preferably 600 nm, even more preferably from 300 nm to 500 nm, and most preferably from 300 nm to 400 nm.
  • the volume resistivity value is 10 ⁇ cm or less, preferably 7 ⁇ cm or less, and more preferably 4 ⁇ cm or less. Further, the lower limit of the volume resistance value is 1.47 ⁇ cm. Further, the volume shrinkage rate is 10% or more, more preferably 13% or more, and even more preferably 15% or more. Further, the upper limit of the volume shrinkage rate is 40%.
  • the particle size of silver fine particles measured by the BET method is as described above.
  • silver fine particles are formed into cylindrical pellets, the pellets are placed in an electric furnace, and fired at a temperature of 150° C. for 1 hour in a nitrogen atmosphere.
  • Pellets are produced by holding silver fine particles at a pressure of 127 MPa for 10 seconds using a press machine.
  • the volume resistivity value is a value obtained by measuring with a four-probe method using pellets.
  • Loresta EP MCP-T360
  • Mitsubishi Chemical Corporation is used as the measuring device.
  • volume shrinkage rate was determined by holding silver fine particles for 10 seconds at a pressure of 127 MPa using a press machine as described above to produce a cylindrical pellet, and measuring the thickness and diameter of the cylindrical pellet with a caliper. This is a value calculated from the volume of pellets before and after firing.
  • the silver fine particles have a particle size of 0.1 ⁇ m or more and 1 ⁇ m or less as measured by the BET method, and have a volume resistivity of 10 ⁇ cm or less after being fired in a pellet form at a temperature of 150° C. for 1 hour in a nitrogen atmosphere, and When the volumetric shrinkage rate is 10% or more, the volumetric shrinkage is large and the conductivity is high. Furthermore, silver particles have a higher melting point than solder and the like, and have excellent heat resistance. Therefore, when silver fine particles are used as a bonding material, it is possible to achieve excellent electrical conductivity while satisfying heat resistance.
  • the silver fine particles have a particle size of 0.1 ⁇ m or more and 1 ⁇ m or less as measured by the BET method, a volume resistivity of 10 ⁇ cm or less after being fired in the air as a pellet at a temperature of 150° C. for 1 hour, and a volume of The shrinkage rate is 5% or more.
  • the atmosphere refers to an atmosphere generally referred to as air. What is in the atmosphere is also called the atmospheric atmosphere.
  • the composition of the air is 78.08% by volume of nitrogen, 20.95% by volume of oxygen, 0.93% by volume of argon, and 0.03% by volume of carbon dioxide. Note that general measurement errors are allowed for the composition of air.
  • the particle size of the silver fine particles is preferably 100 to 600 nm because of the ease of handling during dispersion and the small volume shrinkage after being fired in the air (atmospheric atmosphere) for 1 hour in the form of pellets. , 300 nm to 600 nm is more preferable, 300 nm to 500 nm is even more preferable, and 300 nm to 400 nm is most preferable.
  • the volume resistivity value is preferably 8 ⁇ cm or less, more preferably 7 ⁇ cm or less, and most preferably 5 ⁇ cm or less.
  • the lower limit of the volume resistance value is 1.47 ⁇ cm.
  • the volume shrinkage rate is 5% or more, preferably 6% or more, and more preferably 7% or more.
  • the upper limit of the volume shrinkage rate is 40%.
  • the particle size of silver fine particles measured by the BET method is as described above.
  • volume resistivity value is a value obtained by measuring with a four-probe method using pellets.
  • Loresta EP MCP-T360
  • Mitsubishi Chemical Corporation is used as the measuring device.
  • volume shrinkage rate was determined by holding silver fine particles for 10 seconds at a pressure of 127 MPa using a press machine as described above to produce a cylindrical pellet, and measuring the thickness and diameter of the cylindrical pellet with a caliper. This is a value calculated from the volume of pellets before and after firing.
  • the silver fine particles have a particle size of 0.1 ⁇ m or more and 1 ⁇ m or less as measured by the BET method, a volume resistivity of 10 ⁇ cm or less after being fired in the air as a pellet at a temperature of 150° C. for 1 hour, and a volume of When the shrinkage rate is 5% or more, the volumetric shrinkage is large and the conductivity is high. Furthermore, silver particles have a higher melting point than solder and the like, and have excellent heat resistance. Therefore, when silver fine particles are used as a bonding material, it is possible to achieve excellent electrical conductivity while satisfying heat resistance.
  • each of the above-mentioned silver particles be coated with an aliphatic amine.
  • the aliphatic amine is present as a surface coating on silver particles.
  • the aliphatic amine preferably has 10 to 18 carbon atoms, more preferably 12 to 16 carbon atoms, because it has a large volumetric contraction and high conductivity.
  • Aliphatic amines include dodecylamine and hexadecylamine. Dodecylamine and hexadecylamine have a linear structure. Note that the presence or absence of surface coating and the composition of silver fine particles can be examined using, for example, FT-IR (Fourier transform infrared spectrophotometer).
  • FIG. 1 is a schematic diagram showing one example of the usage of the silver fine particles of the present invention
  • FIG. 2 is a schematic diagram showing another example of the usage of the silver fine particles of the present invention.
  • the silver particles are used, for example, to bond the substrate 50 and the power semiconductor element 52 shown in FIG.
  • Silver fine particles are used for die attachment.
  • the silver particles constitute a joint 54 that joins the substrate 50 and the power semiconductor element 52.
  • the bonding portion 54 is formed by firing the silver particles at a temperature of 100° C. or 150° C. for 1 hour in a nitrogen atmosphere or in the air, for example.
  • the substrate 50 and the power semiconductor element 52 are bonded to each other by the bonding portion 54, and the substrate 50 and the power semiconductor element 52 are physically fixed. It is also used to bond one substrate 50 shown in FIG. 2 with a plurality of semiconductor elements.
  • three semiconductor elements 53 are illustrated.
  • the three semiconductor elements 53 have different heights.
  • the three semiconductor elements 53 are bonded to the substrate 50 via bonding portions 54
  • Silver fine particles have a higher melting point and higher heat resistance than solder and resin. Further, as mentioned above, the silver fine particles have a volume resistivity of 15 ⁇ cm or less and a volume shrinkage rate of 5% or more, for example, 40% after being fired in the form of pellets at a temperature of 100° C. for 1 hour in a nitrogen atmosphere. It is as follows. Further, the silver fine particles have a volume resistivity of 10 ⁇ cm or less and a volume shrinkage of 10% or more, for example, 40% or less after being fired in the form of pellets at a temperature of 150° C. for 1 hour in a nitrogen atmosphere.
  • the silver fine particles have a volume resistivity of 10 ⁇ cm or less and a volume shrinkage of 5% or more, for example, 40% or less after being fired in the form of pellets at a temperature of 150° C. for 1 hour in the atmosphere. For these reasons, even if a temperature change occurs due to the operation of the power semiconductor element 52, the volume variation of the joint portion 54 is small, and the occurrence of cracks and the like is suppressed. This maintains the bond and provides high durability. Further, since the silver fine particles have a low volume resistivity after firing, they have excellent thermal conductivity, and the heat generated in the power semiconductor element 52 can be efficiently conducted to the substrate 50 through the bonding portion 54.
  • the distance to the substrate 50 is different between a short semiconductor element and a tall semiconductor element. Since the volumetric shrinkage rate is large, when the substrate 50 is pressurized to bond with a short semiconductor element, excessive pressure is not applied even to a tall semiconductor element.
  • bonding the three semiconductor elements 53 having different heights as shown in FIG. By using silver fine particles with a large volumetric shrinkage rate as a bonding material and using a bonding material with a small volumetric shrinkage rate in a wide area, the plurality of semiconductor elements 53 can be uniformly pressurized and sufficient bonding can be maintained.
  • the substrate 50 is, for example, a ceramic substrate made of Si 3 N 4 or the like provided with copper wiring.
  • the power semiconductor element 52 is a semiconductor element using a semiconductor such as silicon carbide (SiC), gallium nitride (GaN), gallium oxide, or diamond, for example.
  • the semiconductor element 53 is a semiconductor element using a general silicon substrate. Note that the semiconductor element 53 may be a power semiconductor element.
  • the silver particles are not limited to bonding with the power semiconductor element 52 or the semiconductor element 53, but can also be used in bonding with a high frequency device, a light emitting diode, a semiconductor laser, or the like. As mentioned above, silver particles have excellent thermal conductivity and are suitable for bonding to items that generate a large amount of heat or have a high operating temperature. In addition to bonding, silver fine particles can also be used for various types of wiring such as signal wiring and conductive wiring.
  • FIG. 3 is a schematic diagram showing an example of an apparatus for producing silver particles of the present invention.
  • the silver fine particles described above can be obtained by the silver fine particle manufacturing apparatus 10 (hereinafter simply referred to as the manufacturing apparatus 10) shown in FIG.
  • the manufacturing device 10 includes a plasma torch 12 that generates a thermal plasma flame, a material supply device 14 that supplies raw material powder for silver particles into the plasma torch 12, and a cooling tank that serves as a cooling tank for producing primary silver particles 15.
  • the chamber 16 and the cyclone 19 are connected by a connecting pipe 21a.
  • the manufacturing apparatus 10 further includes a supply unit 40 that supplies a surface treatment agent to the primary silver particles 15 or the secondary silver particles 18.
  • the primary silver particles 15 and the secondary silver particles 18 are both particulate bodies that are in the process of being manufactured as particulates of the present invention.
  • the fine particles of the present invention are those obtained by surface-treating the primary silver particles 15 or the secondary silver particles 18, that is, the surface-treated silver particles 30.
  • the surface of the silver particles 30 is coated with aliphatic amine.
  • various devices described in Japanese Patent Application Laid-open No. 2007-138287 can be used, for example.
  • silver powder for example, is used as a raw material for producing the fine particles.
  • the average particle size of the silver powder is appropriately set so that it can be easily evaporated in a hot plasma flame.
  • the average particle size of the silver powder is measured using a laser diffraction method, and is, for example, 100 ⁇ m or less, preferably 50 ⁇ m or less, and more preferably 15 ⁇ m or less.
  • the plasma torch 12 is composed of a quartz tube 12a and a high-frequency oscillation coil 12b surrounding the outside of the quartz tube 12a.
  • a supply pipe 14a which will be described later, is provided at the center of the upper part of the plasma torch 12 for supplying fine particle raw material powder into the plasma torch 12.
  • a plasma gas supply port 12c is formed around the supply pipe 14a (on the same circumference), and the plasma gas supply port 12c is ring-shaped.
  • a power source (not shown) that generates a high frequency voltage is connected to the high frequency oscillation coil 12b. When a high frequency voltage is applied to the high frequency oscillation coil 12b, a thermal plasma flame 24 is generated. The thermal plasma flame 24 evaporates raw materials (not shown) into a gaseous mixture.
  • the plasma torch 12 is a processing unit that converts raw materials into a gas phase mixture using a gas phase method.
  • the plasma gas supply unit 22 supplies plasma gas into the plasma torch 12.
  • the plasma gas supply section 22 is connected to the plasma gas supply port 12c via a pipe 22a.
  • the plasma gas supply section 22 is provided with a supply amount adjustment section such as a valve for adjusting the supply amount.
  • Plasma gas is supplied into the plasma torch 12 from the plasma gas supply section 22 through the ring-shaped plasma gas supply port 12c in the direction shown by arrow P and the direction shown by arrow S.
  • a mixed gas of hydrogen gas and argon gas is used as the plasma gas.
  • hydrogen gas and argon gas are stored in the plasma gas supply section 22.
  • Hydrogen gas and argon gas are supplied from the plasma gas supply unit 22 into the plasma torch 12 from the direction shown by arrow P and the direction shown by arrow S via piping 22a and plasma gas supply port 12c.
  • argon gas may be supplied in the direction indicated by arrow P.
  • a plasma gas is used that is appropriate for the silver particles, it is not essential to use a mixed gas as the plasma gas as described above, and one type of gas may be used as the plasma gas.
  • the temperature of the thermal plasma flame 24 needs to be higher than the boiling point of the raw material powder.
  • the temperature of the thermal plasma flame 24 can be set to 6000°C, and theoretically it is thought to reach about 10000°C.
  • the pressure atmosphere in the plasma torch 12 is below atmospheric pressure.
  • the atmosphere below atmospheric pressure is not particularly limited, but is, for example, 0.5 to 100 kPa.
  • the outside of the quartz tube 12a is surrounded by a concentric tube (not shown), and cooling water is circulated between this tube and the quartz tube 12a to cool the quartz tube 12a. This prevents the quartz tube 12a from becoming too hot due to the thermal plasma flame 24 generated within the plasma torch 12.
  • the material supply device 14 is connected to the upper part of the plasma torch 12 via a supply pipe 14a.
  • the material supply device 14 supplies raw materials to a thermal plasma flame 24 within the plasma torch 12 .
  • the material supply device 14 is not particularly limited as long as it can supply the raw material into the thermal plasma flame 24, and for example, it supplies the raw material into the thermal plasma flame 24 in a state where the raw material is dispersed in the form of particles.
  • the material supply device 14 includes, for example, a storage tank (not shown) for storing raw materials, a screw feeder (not shown) for conveying a fixed amount of raw materials, and a final dispersion of the raw materials conveyed by the screw feeder. It has a dispersion section (not shown) that disperses the particles into a state of primary particles before being mixed, and a carrier gas supply source (not shown).
  • the raw material is supplied to the thermal plasma flame 24 in the plasma torch 12 through the supply pipe 14a along with the carrier gas to which extrusion pressure is applied from the carrier gas supply source.
  • the structure of the material supply device 14 is not particularly limited as long as it can prevent the raw materials from agglomerating and spread the raw materials into the plasma torch 12 while maintaining a dispersed state.
  • an inert gas such as argon gas is used as the carrier gas.
  • the carrier gas flow rate can be controlled using, for example, a flow meter such as a float type flow meter. Further, the flow rate value of the carrier gas refers to the scale value of the flow meter.
  • the chamber 16 is provided below and adjacent to the plasma torch 12, and within the chamber 16, primary fine silver particles 15, which are fine particles, are collected from the above-mentioned mixture in a gas phase without using a cooling gas. generated. Further, the chamber 16 functions as a cooling tank. Note that the cooling gas is also called quenching gas, and argon gas or the like is used.
  • the gas supply unit 28 supplies, for example, a temperature adjustment gas containing an inert gas into the connecting pipe 21a or the connecting pipe 21b.
  • the gas supply unit 28 supplies a temperature adjustment gas containing an inert gas to the primary silver particles 15 or the secondary silver particles 18 .
  • the gas supply section 28 includes, for example, a valve 28a, and a first gas supply pipe 28b and a second gas supply pipe 28c connected to the valve 28a.
  • the first gas supply pipe 28b is connected to the connecting pipe 21a
  • the second gas supply pipe 28c is connected to the connecting pipe 21b.
  • the gas supply unit 28 further includes a pressure applying device (not shown) such as a compressor or a blower that applies extrusion pressure to the temperature adjustment gas supplied to the first gas supply pipe 28b or the second gas supply pipe 28c. Further, the gas supply unit 28 includes a storage unit (not shown) that stores temperature adjustment gas and a pressure control valve that controls the amount of gas supplied.
  • the temperature adjustment gas is, for example, argon gas. The temperature adjusting gas supplied from the gas supply section 28 into the connecting pipe 21a or the connecting pipe 21b allows adjustment to a desired gas temperature.
  • the chamber 16 is provided with a cyclone 19 for classifying the primary silver particles 15 into desired particle sizes.
  • the cyclone 19 includes an inlet pipe 19a that supplies primary particles 15 from the chamber 16, a cylindrical outer cylinder 19b connected to the inlet pipe 19a and located at the upper part of the cyclone 19, and a cylindrical outer cylinder 19b that extends downward from the lower part of the outer cylinder 19b.
  • a truncated cone section 19c that continues toward the side and gradually decreases in diameter; and a coarse particle recovery section that is connected to the lower side of the truncated cone section 19c and collects coarse particles having a particle size equal to or larger than the above-mentioned desired particle size.
  • the connecting pipe 21a is a transport path for the primary fine particles 15.
  • An airflow containing primary fine particles 15 is blown from the inlet pipe 19a of the cyclone 19 along the inner circumferential wall of the outer cylinder 19b, and as a result, this airflow flows inside the outer cylinder 19b as shown by arrow T in FIG.
  • a downward swirling flow is formed by flowing from the peripheral wall toward the truncated cone portion 19c.
  • the coarse particles are unable to ride the upward flow due to the balance between centrifugal force and drag, and descend along the side surface of the truncated cone portion 19c.
  • the particles are collected in the coarse particle collection chamber 19d. Further, the particles that are more affected by drag than by centrifugal force are discharged to the outside of the cyclone 19 through the inner pipe 19e and the connecting pipe 21b with an upward flow on the inner wall of the truncated cone portion 19c.
  • negative pressure suction force
  • the fine particles separated from the above-mentioned swirling airflow are suctioned as indicated by the symbol U, and are sent to the collection section 20 through the inner pipe 19e and the connecting pipe 21b.
  • a collection section 20 is provided on an extension of the inner tube 19e, which is the outlet of the airflow within the cyclone 19, for collecting silver fine particles 30 having a desired particle size on the nanometer order.
  • the recovery unit 20 includes a recovery chamber 20a, a filter 20b provided within the recovery chamber 20a, and a vacuum pump 29 connected via a pipe provided below within the recovery chamber 20a.
  • the silver particles 30 sent from the cyclone 19 are drawn into the collection chamber 20a by suction by the vacuum pump 29, and are collected while remaining on the surface of the filter 20b.
  • the number of cyclones used is not limited to one, but may be two or more, or no cyclones may be used.
  • the supply unit 40 supplies the surface treatment agent St to the silver particles within the chamber 16, downstream of the first gas supply pipe 28b in the connection pipe 21a, or downstream of the second gas supply pipe 28c in the connection pipe 21b. It is something.
  • the surface treatment agent St forms silver particles whose surfaces are coated with aliphatic amine.
  • the chamber 16 side with respect to the connecting pipe 21a is referred to as the upstream side
  • the cyclone 19 side is referred to as the downstream side.
  • the supply section 40 includes, for example, a valve 41, and a first supply pipe 41a, a second supply pipe 41b, and a third supply pipe 41c connected to the valve 41.
  • a first supply pipe 41a is connected to the side surface 16b of the chamber 16.
  • the second supply pipe 41b is connected to the connecting pipe 21a downstream of the first gas supply pipe 28b, and the third supply pipe 41c is connected to the connecting pipe 21b downstream of the second gas supply pipe 28c.
  • the first supply pipe 41a is connected, for example, in the chamber 16 at a height comparable to or lower than the position where the connecting pipe 21a is connected.
  • the surface treatment agent St is supplied into the chamber 16 from the inner wall 16a of the chamber 16 via the first supply pipe 41a.
  • the connection position of the third supply pipe 41c in the connection pipe 21b be P2 .
  • the connection position P 2 of the third supply pipe 41c is located downstream of the connection position P 1 of the second supply pipe 41b.
  • the supply unit 40 supplies the surface treatment agent St to the primary silver particles 15 in the chamber 16, the primary silver particles 15 passing through the connecting tube 21a, or the secondary silver particles 18 passing through the connecting tube 21b.
  • the supply unit 40 supplies the surface treatment agent St in a temperature range suitable for the surface treatment agent St.
  • the surface treatment agent St was attached to the primary silver particles 15 or the secondary silver particles 18, and the primary silver particles 15 or the secondary silver particles 18 were surface-treated, and the surface was coated with aliphatic amine. Silver fine particles are formed. Thereby, fusion of the silver particles is prevented, and silver particles 30 are obtained.
  • the method of supplying the surface treatment agent St by the supply unit 40 is not particularly limited, and for example, a method of forming droplets of the surface treatment agent St and spraying them onto the secondary silver particles 18 is exemplified.
  • the surface treatment agent St is supplied at a suitable temperature range.
  • the suitable temperature range is a temperature range in which the surface treatment agent St can play a role of preventing fusion of silver particles. Therefore, as long as fusion of the silver particles can be prevented, it may be introduced from a temperature range where the surface treatment agent St is denatured, or may be introduced from a temperature range where the surface treatment agent St is not denatured.
  • the surface condition of the surface-treated fine particles can be examined using, for example, FT-IR (Fourier transform infrared spectrophotometer).
  • the temperature range that can serve to prevent the above-mentioned fusion of the silver particles is a temperature range in which the primary particles 15 can be coated with the organic substance produced by modification of the surface treatment agent St or with the surface treatment agent St.
  • the above-mentioned temperature range in which the surface treatment agent St does not denature is a temperature range determined based on the temperature measured by differential thermal-thermogravimetric simultaneous measurement (TG-DTA).
  • the temperature range in which the above-mentioned surface treatment agent St does not denature is defined as the temperature range in which the weight reduction rate is 50% by mass or less in simultaneous differential heat-thermogravimetry measurement of the surface treatment agent St.
  • the weight reduction rate is more preferably 30% by mass or less, still more preferably 10% by mass or less.
  • STA7200 (trade name) manufactured by Hitachi High-Tech Science Co., Ltd. is used for the simultaneous differential thermal and thermogravimetric measurement.
  • an aliphatic amine is used as the surface treatment agent St. If the aliphatic amine is liquid in the state of use, it is not necessarily necessary to dissolve it in a solvent such as an aqueous solution, and it can also be used alone.
  • the aliphatic amine preferably has 10 to 18 carbon atoms, more preferably 12 to 16 carbon atoms.
  • Aliphatic amines include dodecylamine and hexadecylamine. Dodecylamine and hexadecylamine have a linear structure.
  • the dodecylamine for example, one manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. (product code 123-00246) can be used.
  • As the hexadecylamine for example, one manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. (product code 038-07162) can be used.
  • the surface treatment agent St may contain an organic solvent.
  • organic solvent is not particularly limited and can be appropriately selected depending on the purpose.
  • organic solvents include alcohols such as ethanol and methanol, ketones such as acetone, alkyl halides, amides such as formamide, sulfoxides such as dimethyl sulfoxide, heterocyclic compounds, hydrocarbons, and ethyl acetate.
  • Examples include esters and ethers. These may be used alone or in combination of two or more.
  • a sensor may be provided to measure the temperature of the conveyance path of the primary silver particles 15 or the secondary silver particles 18.
  • the temperature measurement result of this sensor is used to determine whether the temperature is in a temperature range suitable for the surface treatment agent St.
  • the temperature measurement result is output to the supply unit 40, for example.
  • the supply unit 40 it is possible to determine whether the temperature is in a temperature range suitable for the surface treatment agent St based on the measurement result of the temperature of the conveyance path of the primary silver particles 15 or the secondary silver particles 18 by the sensor. can. If the temperature of the transport path of the primary silver particles 15 or the secondary silver particles 18 is in a temperature range not suitable for the surface treatment agent St, for example, the flow rate of the temperature adjustment gas supplied from the gas supply unit 28 is changed.
  • the temperature measurement result of the sensor is used to determine whether the temperature range is suitable for the surface treatment agent St. Therefore, the sensor detects the connection position P 1 of the second supply pipe 41b in the connection pipe 21a. It is preferable to provide it upstream. For this reason, the sensor is provided, for example, in the connecting pipe 21a.
  • the configuration of the sensor is not particularly limited as long as it can measure temperature, but it is preferable that the measurement time is short. Therefore, for example, a resistance thermometer, a radiation thermometer, an infrared radiation temperature sensor, a thermistor, or the like can be used as the sensor.
  • raw material powder for silver fine particles for example, silver powder having an average particle diameter of 15 ⁇ m or less is charged into the material supply device 14 .
  • argon gas and hydrogen gas are used as the plasma gas, and a high frequency voltage is applied to the high frequency oscillation coil 12b to generate a thermal plasma flame 24 within the plasma torch 12.
  • silver powder is transported as a carrier gas using, for example, argon gas, and is supplied into the thermal plasma flame 24 in the plasma torch 12 via the supply pipe 14a.
  • the supplied silver powder is evaporated in the thermal plasma flame 24 to become a gaseous mixture, and primary fine silver particles 15 are generated from the gaseous mixture in the chamber 16 without using a cooling gas. be done.
  • the primary silver particles 15 obtained in the chamber 16 are blown along the inner circumferential wall of the outer cylinder 19b along with the airflow from the inlet pipe 19a of the cyclone 19 through the connection pipe 21a. As shown by the arrow T in FIG. 3, it flows along the inner peripheral wall of the outer cylinder 19b, forming a swirling flow and descending.
  • the coarse particles are unable to ride the upward flow due to the balance between centrifugal force and drag, and descend along the side surface of the truncated cone portion 19c.
  • the particles are collected in the coarse particle collection chamber 19d.
  • the particles that are more affected by the drag force than by the centrifugal force are discharged from the inner wall to the outside of the cyclone 19 along with an upward flow on the inner wall of the truncated cone portion 19c.
  • the discharged secondary silver particles 18 are sucked in the direction indicated by the symbol U in FIG. 3 by the negative pressure (suction force) from the recovery section 20 by the vacuum pump 29, and pass through the inner tube 19e and the connecting tube 21b. do.
  • the temperature adjusting gas is supplied from the gas supply section 28 to the first gas supply tube 28b or the second gas supply tube 28b.
  • the primary silver particles 15 or the secondary silver particles 18 are cooled by being supplied into the connecting tube 21a or 21b through the supply tube 28c.
  • the primary fine silver particles 15 or the secondary fine silver particles 18 are brought into a temperature range suitable for the surface treatment agent using the temperature adjustment gas, they are further transported from the supply section 40 into the chamber 16, into the connecting pipe 21a or into the connecting pipe 21b.
  • the surface treatment agent St is supplied to the primary silver particles 15 or the secondary silver particles 18 in the form of, for example, spraying, and the primary silver particles 15 or the secondary silver particles 18 are surface-treated. Ru.
  • the surface-treated primary silver particles 15 or secondary silver particles 18, that is, the silver particles 30, are sent to the recovery section 20, and the silver particles 30 are recovered by the filter 20b of the recovery section 20. In this way, silver fine particles are obtained.
  • the internal pressure within the cyclone 19 is preferably equal to or lower than atmospheric pressure.
  • the particle size of the silver fine particles 30 is determined to be an arbitrary particle size on the order of nanometers depending on the purpose.
  • primary fine particles of silver are formed using a thermal plasma flame as a heat source, but primary fine particles of silver may also be formed using other vapor phase methods. Therefore, as long as it is a gas phase method, the method is not limited to using a thermal plasma flame, and for example, a manufacturing method in which primary fine particles of silver are formed by a flame method may be used. Note that a method for producing primary particles using a thermal plasma flame is referred to as a thermal plasma method.
  • the flame method is a method of synthesizing fine particles by passing a raw material containing silver through the flame using flame as a heat source.
  • a raw material containing silver is supplied to a flame and silver particles are generated in the flame to obtain primary silver particles 15.
  • the surface treatment agent St is supplied to the primary silver particles 15 or the secondary silver particles 18 to produce silver particles. Note that in the flame method, the same surface treatment agent as in the above-mentioned thermal plasma method can be used.
  • the present invention is basically configured as described above. Although the silver particles of the present invention have been described in detail above, the present invention is not limited to the above-described embodiments, and it goes without saying that various improvements or changes may be made without departing from the gist of the present invention. be.
  • silver particles of the present invention will be explained in more detail.
  • silver fine particles of Examples 1 and 2 and silver fine particles of Comparative Example 1 were manufactured.
  • a production apparatus 10 shown in FIG. 3 was used to produce the silver particles of Examples 1 and 2 and the silver particles of Comparative Example 1. The manufacturing conditions are shown below.
  • Example 1 silver powder with an average particle size of 15 ⁇ m was used as the raw material powder.
  • the average particle size of the silver powder is a value measured using a particle size distribution meter.
  • MT3300 manufactured by Microtrac Bell Co., Ltd. was used. Note that the manufacturing conditions for the silver particles were such that the input to the plasma was constant at 18 kW, and the pressure inside the plasma torch was fixed at 60 kPa.
  • Argon gas was used as a carrier gas. The flow rate of argon gas was set to 5 liters/min (converted to standard conditions). Argon gas and hydrogen gas were used as plasma gas.
  • the flow rate of argon gas was 200 liters/min (converted to standard conditions), and the flow rate of hydrogen gas was 5 liters/min (converted to standard conditions).
  • Argon gas was used as the temperature adjustment gas.
  • the flow rate of argon gas was set to 380 liters/min (converted to standard conditions).
  • dodecylamine was used as the surface treatment agent. Using ethanol as a solvent, a solution containing dodecylamine (concentration of dodecylamine 10.0 W/W%) was sprayed onto the primary silver particles from the third supply pipe 41c (see FIG. 3) using atomizing gas. .
  • Argon gas was used as the atomizing gas. Note that dodecylamine manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. (product code 123-00246) was used. Ethanol manufactured by Junsei Kagaku Co., Ltd. (product code 17065-1283) was used.
  • Example 2 differs from Example 1 in that hexadecylamine was used as the surface treatment agent.
  • a solution containing hexadecylamine (concentration of hexadecylamine 10.0 W/W%) was supplied to silver from the third supply pipe 41c (see FIG. 3) using a spray gas. was sprayed onto primary fine particles.
  • Argon gas was used as the atomizing gas.
  • the flow rate of argon gas used as the temperature adjustment gas was 500 liters/min (converted to standard conditions).
  • the hexadecylamine manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. (product code 038-07162) was used. Ethanol manufactured by Junsei Kagaku Co., Ltd. (product code 17065-1283) was used.
  • Comparative Example 1 is different from Example 1 except that the surface treatment agent is different, the surface treatment agent is supplied from the second supply pipe 41b (see FIG. 3), and the flow rate of the temperature adjustment gas is different.
  • Comparative Example 1 used citric acid. Using pure water as a solvent, an aqueous solution containing citric acid (concentration of citric acid 3.76 W/W%) is sprayed onto primary fine silver particles from the second supply pipe 41b (see FIG. 3) using a spray gas. did.
  • Argon gas was used as the atomizing gas. The flow rate of argon gas as the temperature adjustment gas was set to 500 liters/min (converted to standard conditions).
  • SEM images were obtained for the silver particles of Examples 1 and 2.
  • the SEM image was obtained using Regulus 8220 manufactured by Hitachi High-Technologies Corporation.
  • a SEM image of the silver fine particles of Example 1 is shown in FIG. 4, and a SEM image of the silver fine particles of Example 2 is shown in FIG. Macsorb HM-1208 manufactured by Mountech Co., Ltd. was used to measure the particle diameters of the silver fine particles of Examples 1 and 2 and the silver fine particles of Comparative Example 1 by the BET method.
  • the value and volume shrinkage were measured.
  • the results are shown in Table 1 below.
  • the nitrogen atmosphere was such that nitrogen gas with a purity of 99.99 (nitrogen 99.99 volume %) was constantly flowing, and the oxygen concentration was 100 volume ppm or less.
  • the oxygen concentration was measured using a low concentration oxygen analyzer PS-820-L manufactured by Iijima Electronics Co., Ltd.
  • In measuring the volume resistivity value first, silver particles were held at a pressure of 127 MPa for 10 seconds using a press machine to produce cylindrical pellets.
  • volumetric shrinkage rate 100 - ((volume after firing/volume before firing) x 100) Note that the density was measured as follows.
  • Measure the thickness and diameter of the cylindrical pellet before firing with calipers measure the mass of the pellet with an electronic balance, and calculate the density of the cylindrical pellet before firing from the volume and mass of the cylindrical pellet. Calculated.
  • the thickness and diameter of the cylindrical pellet after firing were measured using calipers, the mass of the pellet was measured using an electronic balance, and from the volume and mass of the cylindrical pellet after firing, the cylindrical shape after firing was determined. The density of the pellet was calculated.
  • the silver particles of Examples 1 and 2 had larger particle sizes than the silver particles of Comparative Example 1. After forming the silver particles of Examples 1 and 2 into cylindrical pellets and firing them at a temperature of 100° C. for 1 hour in a nitrogen atmosphere, the volume resistivity was smaller than that of the silver particles of Comparative Example 1. And the volumetric shrinkage rate is large.
  • Example 10 Example 10 was the same as Example 1 of the first example.
  • Example 11 differs from Example 1 in the first example in that the internal pressure of the plasma torch is 85 kPa, the concentration of dodecylamine is 1.5 W/W%, and the temperature adjustment gas is argon gas. The procedure was the same as in Example 1 except that the flow rate was 150 liters/min (converted to standard conditions).
  • Example 12 Example 12 was the same as Example 2 of the first example.
  • Example 13 is the same as Example 2 of the first example except that the internal pressure of the plasma torch is 85 kPa and the concentration of hexadecylamine is 1.5 W/W%. It was the same.
  • Comparative Example 10 was the same as Comparative Example 1 of the first example.
  • SEM images (not shown) were obtained for the silver particles of Examples 10 to 13.
  • the SEM image was obtained using Regulus 8220 manufactured by Hitachi High-Technologies Corporation. It has been confirmed that the silver particles of Examples 10 to 13 are the same as the silver particles of Example 1 shown in FIG. 4 and the silver particles of Example 2 shown in FIG. 5 described above.
  • Macsorb HM-1208 manufactured by Mountech Co., Ltd. was used to measure the particle sizes of the silver fine particles of Examples 10 to 13 and the silver fine particles of Comparative Example 10 by the BET method.
  • the silver fine particles of Examples 10 to 13 and the silver fine particles of Comparative Example 10 were formed into cylindrical pellets and the volume resistivity values before firing were determined. After firing in a nitrogen atmosphere at a temperature of 150° C. for 1 hour, the volume resistivity and volume shrinkage were measured. The results are shown in Table 2 below. Note that the nitrogen atmosphere was the same as in the first embodiment described above. The volume resistivity value was measured in the same manner as in the first example described above. The density was also measured in the same manner as in the first example described above. The pellets were placed in an electric furnace and fired at a temperature of 150° C. for 1 hour in a nitrogen atmosphere.
  • the volumetric shrinkage rate was measured in the same manner as in the first example described above.
  • the pellets were placed in an electric furnace and fired at a temperature of 150° C. for 1 hour in a nitrogen atmosphere.
  • the silver particles of Examples 10 to 13 had larger particle sizes than the silver particles of Comparative Example 10. After forming the silver particles of Examples 10 to 13 into cylindrical pellets and firing them at a temperature of 150° C. for 1 hour in a nitrogen atmosphere, the silver particles of Examples 10 to 13 had a lower volume resistivity value than the silver particles of Comparative Example 10. It was possible to achieve both a high volumetric shrinkage rate.
  • Example 3 fine silver particles of Examples 20 to 25 and fine silver particles of Comparative Examples 20 to 22 were produced.
  • a production apparatus 10 shown in FIG. 3 was used to produce the silver particles of Examples 20 to 25 and the silver particles of Comparative Examples 20 to 22. The manufacturing conditions are shown below.
  • Example 20 Example 20 was the same as Example 1 of the first example.
  • Example 21 differs from Example 1 in the first example in that the pressure inside the plasma torch is 85 kPa, the concentration of dodecylamine is 0.5 W/W%, and the temperature adjustment gas is argon gas. The procedure was the same as in Example 1 except that the flow rate was 150 liters/min (converted to standard conditions).
  • Example 22 Example 22 was the same as Example 11 of the second example.
  • Example 23 was the same as Example 2 of the first example.
  • Example 24 is different from Example 2 of the first example in that the internal pressure of the plasma torch is 85 kPa, the concentration of hexadecylamine is 0.5 W/W%, and the temperature adjustment gas is argon gas. The procedure was the same as in Example 2 except that the flow rate was 150 liters/min (converted to standard conditions).
  • Example 25 was the same as Example 13 of the second example.
  • Comparative Example 20 differs from Example 1 of the first example in that a cooling gas was used, the surface treatment agent was different, and the surface treatment agent was supplied from the first supply pipe 41a (see FIG. 3). , was the same as Example 1 except that no temperature adjustment gas was used.
  • Argon gas and methane gas were used as cooling gas.
  • the flow rate of argon gas was 800 liters/minute (converted to standard conditions), and the flow rate of methane gas was 1 liter/minute (converted to standard conditions).
  • Comparative Example 20 used citric acid as the organic acid.
  • an aqueous solution containing citric acid (citric acid concentration 18.8 W/W%) is sprayed onto primary silver particles using a spray gas from the first supply pipe 41a (see FIG. 3). did.
  • Argon gas was used as the atomizing gas.
  • Comparative Example 21 differs from Comparative Example 20 in that no cooling gas is used, the concentration of citric acid is 3.76 W/W%, and the surface treatment agent is supplied to the second supply pipe 41b (see FIG. 3).
  • the procedure was the same as Comparative Example 20, except that the gas was supplied from the gas and the temperature adjustment gas was used.
  • the flow rate of argon gas as the temperature adjustment gas was set to 240 liters/min (converted to standard conditions).
  • Comparative example 22 Comparative Example 22 was the same as Comparative Example 21 except that the internal pressure of the plasma torch was 85 kPa and the flow rate of the temperature adjustment gas was different.
  • the flow rate of argon gas as the temperature adjustment gas was set to 15 liters/min (converted to standard conditions).
  • SEM images (not shown) were obtained for the silver particles of Examples 20 to 25.
  • the SEM image was obtained using Regulus 8220 manufactured by Hitachi High-Technologies Corporation. It has been confirmed that the silver particles of Examples 20 to 25 are the same as the silver particles of Example 1 shown in FIG. 4 and the silver particles of Example 2 shown in FIG. 5.
  • Macsorb HM-1208 manufactured by Mountech Co., Ltd. was used to measure the particle diameters of the silver fine particles of Examples 20 to 25 and Comparative Examples 20 to 22 by the BET method.
  • the silver fine particles of Examples 20 to 25 and the silver fine particles of Comparative Examples 20 to 22 were formed into cylindrical pellets, and the volume resistivity before firing was Then, the volume resistivity and volume shrinkage rate were measured after firing in the atmosphere (that is, in the air) at a temperature of 150° C. for 1 hour.
  • the results are shown in Table 3 below. Note that the composition of the atmosphere (air) is as described above.
  • the volume resistivity value was measured in the same manner as in the first example described above.
  • the density was also measured in the same manner as in the first example described above.
  • the pellets were placed in an electric furnace and fired in the atmosphere at a temperature of 150° C. for 1 hour.
  • the volumetric shrinkage rate was measured in the same manner as in the first example described above.
  • the pellets were placed in an electric furnace and fired in the atmosphere at a temperature of 150° C. for 1 hour.
  • the silver particles of Examples 20 to 25 had generally larger particle sizes than the silver particles of Comparative Examples 20 to 22.
  • the silver particles of Examples 20 to 25 had a lower volume resistivity than the silver particles of Comparative Examples 20 to 22 after being formed into cylindrical pellets and fired in the air at a temperature of 150°C for 1 hour. and a high volumetric shrinkage rate.
  • Silver fine particle manufacturing device 12 Plasma torch 12a Quartz tube 12b High-frequency oscillation coil 12c Plasma gas supply port 14 Material supply device 14a Supply pipe 15 Primary fine particles 16 Chamber 16a Inner wall 16b Side surface 18 Secondary fine particles 19 Cyclone 19a Inlet tube 19b Outer tube 19c truncated cone 19d Coarse particle collection chamber 19e Inner pipe 20 Collection section 20a Collection chamber 20b Filter 21a, 21b Connecting tube 22 Plasma gas supply section 22a Piping 24 Hot plasma flame 28 Gas supply section 28a Valve 28b First gas supply pipe 28c Second gas Supply pipe 29 Vacuum pump 30 Silver particles 40 Supply part 41 Valve 41a First supply pipe 41b Second supply pipe 41c Third supply pipe 50 Substrate 52 Power semiconductor element 53 Semiconductor element 54 Joint part St Surface treatment agent

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JP2019108610A (ja) * 2017-12-15 2019-07-04 Ｄｏｗａエレクトロニクス株式会社 球状銀粉およびその製造方法
WO2021039361A1 (ja) * 2019-08-26 2021-03-04 京セラ株式会社 銀粒子、銀粒子の製造方法、ペースト組成物及び半導体装置並びに電気・電子部品
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WO2022045263A1 (ja) * 2020-08-31 2022-03-03 株式会社大阪ソーダ 導電性接着剤
JP2023057992A (ja) * 2021-10-12 2023-04-24 日清エンジニアリング株式会社 銀微粒子

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