WO2016063941A1 - 導電性粒子、導電材料及び接続構造体 - Google Patents

導電性粒子、導電材料及び接続構造体 Download PDF

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Publication number
WO2016063941A1
WO2016063941A1 PCT/JP2015/079816 JP2015079816W WO2016063941A1 WO 2016063941 A1 WO2016063941 A1 WO 2016063941A1 JP 2015079816 W JP2015079816 W JP 2015079816W WO 2016063941 A1 WO2016063941 A1 WO 2016063941A1
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Prior art keywords
conductive
particles
conductive portion
core
connection
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PCT/JP2015/079816
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English (en)
French (fr)
Japanese (ja)
Inventor
暁舸 王
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積水化学工業株式会社
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to CN201580044245.7A priority Critical patent/CN106605273A/zh
Priority to KR1020167027605A priority patent/KR20170072169A/ko
Priority to JP2015555877A priority patent/JPWO2016063941A1/ja
Priority to KR1020227009140A priority patent/KR20220041240A/ko
Publication of WO2016063941A1 publication Critical patent/WO2016063941A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • 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
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations

Definitions

  • the present invention relates to conductive particles having base particles and conductive portions arranged on the outer surface of the base particles.
  • the present invention also relates to a conductive material and a connection structure using the conductive particles.
  • Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known.
  • anisotropic conductive material conductive particles are dispersed in a binder resin.
  • the anisotropic conductive material may be connected between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), or connected between a semiconductor chip and a flexible printed circuit board (COF ( (Chip on Film)), connection between a semiconductor chip and a glass substrate (COG (Chip on Glass)), connection between a flexible printed circuit board and a glass epoxy substrate (FOB (Film on Board)), and the like.
  • FOG Glass
  • COF Chip on Film
  • Patent Document 1 listed below includes base material particles, a copper layer provided on the outer surface of the base material particle, and a palladium layer provided on the outer surface of the copper layer.
  • the electroconductive particle provided with these is disclosed.
  • the average thickness of the palladium layer is 5 nm or more.
  • the palladium layer is formed using a plating solution containing a hydrazine compound as a reducing agent.
  • Examples 8 to 10 of Patent Document 1 conductive particles having a plurality of protrusions formed on the outer surface of the palladium layer are disclosed.
  • metallic nickel particles are used as a core material.
  • the conductive particles may not sufficiently contact the electrode. This may increase the connection resistance between the electrodes.
  • an oxide film is often formed on the surfaces of the conductive portion and the electrode. This oxide film may interfere with the contact between the conductive portion and the electrode.
  • connection resistance may be increased. Furthermore, when a connection structure in which electrodes are connected using conductive particles is stored or used for a long time, the connection resistance may be increased. This is because the corrosion of the conductive particles proceeds due to the influence of acid or the like.
  • the base particle on the outer surface of the base particle, includes a first conductive part containing copper, a second conductive part containing palladium, and a plurality of core substances.
  • the first conductive portion is disposed on the outer surface of the first conductive portion
  • the second conductive portion is disposed on the outer surface of the first conductive portion
  • the second conductive portion has a plurality of protrusions on the outer surface.
  • the core material is disposed inside the protrusion of the second conductive portion, and the outer surface of the second conductive portion is raised by the core material, and the material of the core material is Unlike nickel, conductive particles are provided in which the material of the core material has a Mohs hardness of greater than 5.
  • the ratio of the total thickness of the first conductive portion and the second conductive portion to the average diameter of the core substance is preferably 0.1 or more and 6 or less. It is preferable that the thickness of the first conductive portion is 20 nm or more and 300 nm or less. It is preferable that the average diameter of the core substance is 20 nm or more and 1000 nm or less.
  • the thickness of the second conductive part is preferably 3 nm or more and 40 nm or less. It is preferable that the first conductive portion has a Vickers hardness of less than 100.
  • the Mohs hardness of the core material is preferably 6 or more.
  • a conductive material including the above-described conductive particles and a binder resin.
  • a first connection target member having a first electrode on the surface
  • a second connection target member having a second electrode on the surface
  • the first connection target member and the A connection portion connecting the second connection target member
  • the material of the connection portion is the conductive particles described above, or a conductive material containing the conductive particles and a binder resin
  • a connection structure is provided in which the first electrode and the second electrode are electrically connected by the conductive particles.
  • the conductive particle according to the present invention includes a base particle, a first conductive part containing copper, a second conductive part containing palladium, and a plurality of core substances, on the outer surface of the base particle.
  • the first conductive portion is disposed on the outer surface of the first conductive portion, and the second conductive portion has a plurality of protrusions on the outer surface.
  • the core material is disposed inside the protrusion of the second conductive portion, the outer surface of the second conductive portion is raised by the core material, and the material of the core material is Unlike nickel, the material of the core material has a Mohs hardness of more than 5, so that when the electrodes are electrically connected, the connection resistance can be lowered, and further, corrosion of the conductive part is difficult to occur. Can do.
  • FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
  • FIG. 3 is a cross-sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention.
  • the conductive particles according to the present invention include base particles, a first conductive part containing copper, a second conductive part containing palladium, and a plurality of core substances.
  • the first conductive portion is disposed on the outer surface of the base particle, and the second conductive portion is disposed on the outer surface of the first conductive portion. ing.
  • the second conductive portion has a plurality of protrusions on the outer surface.
  • the core substance is disposed inside the protrusion of the second conductive part, and the outer surface of the second conductive part is raised by the core substance.
  • the protrusion is formed by the outer surface of the second conductive portion being raised by the core substance.
  • the material of the core substance is different from nickel, and the Mohs hardness of the material of the core substance exceeds 5.
  • the connection resistance can be lowered.
  • An oxide film is often formed on the surface of the electrode.
  • the conductive particles according to the present invention when the electrodes are connected, the protrusion penetrates the oxide film, and the conductive part and the electrode can be sufficiently brought into contact with each other.
  • the above-described configuration according to the present invention makes it difficult to cause corrosion of the conductive portion. Particularly, corrosion of the conductive part can be made difficult to occur in the presence of an acid. Even when the conductive particles are exposed to the presence of an acid, the conductive portion is hardly corroded, so that the performance of the conductive particles can be maintained high.
  • connection resistance can be lowered. Furthermore, when the connection structure in which the electrodes are connected using conductive particles is stored for a long time or used for a long time, it is possible to prevent the connection resistance from increasing. In the present invention, conduction reliability can be improved.
  • the core material is nickel particles
  • corrosion due to acid tends to occur.
  • the conductive portions may have slight cracks or pinholes, and thus the nickel particles are likely to be corroded.
  • corrosion can be suppressed even when the core material is not nickel.
  • FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
  • the conductive particles 1 include substrate particles 2, a first conductive portion 3 (conductive layer) containing copper, a second conductive portion 4 (conductive layer) containing palladium, and a plurality of conductive particles 1. Core material 5 and insulating material 6. In the conductive particle 1, a multilayer conductive portion is formed.
  • the first conductive part 3 is disposed on the outer surface of the base particle 2.
  • the first conductive portion 3 is in contact with the base particle 2.
  • the second conductive portion 4 is disposed on the outer surface of the first conductive portion 3.
  • the second conductive part 4 is in contact with the first conductive part 3.
  • the conductive particle 1 is a coated particle in which the outer surface of the base particle 2 is covered with the first conductive part 3 and the second conductive part 4.
  • the conductive particle 1 has a plurality of protrusions 1 a on the outer surface of the second conductive portion 4.
  • the first conductive portion 3 has a plurality of protrusions 3a on the outer surface.
  • the second conductive portion 4 has a plurality of protrusions 4a on the outer surface.
  • the plurality of core substances 5 are disposed on the outer surface of the base particle 2.
  • the plurality of core materials 5 are disposed inside the first conductive portion 3.
  • the plurality of core materials 5 are embedded inside the first conductive part 3 and the second conductive part 4.
  • the core substance 5 is disposed inside the protrusions 1a, 3a, 4a.
  • the first conductive part 3 and the second conductive part 4 cover a plurality of core substances 5.
  • the second conductive portion 4 covers a plurality of core substances 5 via the first conductive portion 3.
  • the outer surfaces of the first conductive portion 3 and the second conductive portion 4 are raised by the plurality of core materials 5 to form protrusions 1a, 3a, 4a.
  • the outer surface of the second conductive portion 4 is rust-proofed.
  • a rust preventive film (not shown) is formed on the outer surface of the second conductive portion 4.
  • the conductive particles 1 have an insulating material 6 disposed on the outer surface of the second conductive portion 4. At least a part of the outer surface of the second conductive portion 4 is covered with the insulating material 6.
  • the insulating substance 6 is made of an insulating material and is an insulating particle.
  • the electroconductive particle which concerns on this invention may have the insulating substance arrange
  • FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
  • the conductive particle 1 ⁇ / b> A includes base material particles 2, a first conductive part 3 ⁇ / b> A (conductive layer) containing copper, a second conductive part 4 ⁇ / b> A (conductive layer) containing palladium, and a plurality of conductive particles 1 ⁇ / b> A.
  • the first conductive part 3 ⁇ / b> A is disposed on the outer surface of the base particle 2. Between the base particle 2 and the second conductive portion 4A, the first conductive portion 3A is disposed. The second conductive portion 4A is disposed on the outer surface of the first conductive portion 3A.
  • the conductive particle 1A has a plurality of protrusions 1Aa on the outer surface of the second conductive portion 4A.
  • the first conductive portion 3A has no protrusion on the outer surface.
  • the outer surface shape of the first conductive portion 3A is spherical.
  • the second conductive portion 4A has a plurality of protrusions 4Aa on the outer surface.
  • the plurality of core materials 5 are disposed on the outer surface of the first conductive portion 3A.
  • the plurality of core materials 5 are disposed outside the first conductive portion 3A.
  • the plurality of core materials 5 are arranged inside the second conductive portion 4A.
  • the plurality of core materials 5 are embedded inside the second conductive portion 4A.
  • the core substance 5 is disposed inside the protrusions 1Aa and 4Aa.
  • the second conductive portion 4 ⁇ / b> A covers a plurality of core materials 5.
  • the outer surface of the second conductive portion 4A is raised by the plurality of core materials 5, and the protrusions 1Aa and 4Aa are formed.
  • the core substance may be disposed outside the first conductive portion.
  • the arrangement position of the core substance is not particularly limited as long as it is arranged inside the protrusion of the second conductive portion.
  • the core substance may be disposed inside or inside the second conductive part.
  • the conductive particle 1A has an insulating material 6 disposed on the outer surface of the second conductive portion 4A. At least a part of the outer surface of the second conductive portion 4 ⁇ / b> A is covered with the insulating material 6.
  • (meth) acryl means one or both of “acryl” and “methacryl”
  • (meth) acrylate means one or both of “acrylate” and “methacrylate”. means.
  • the substrate particles include resin particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, and metal particles.
  • the substrate particles are preferably substrate particles excluding metal particles, and more preferably resin particles, inorganic particles excluding metal particles, or organic-inorganic hybrid particles.
  • the base particles may be core-shell particles.
  • the base material particles are more preferably resin particles or organic-inorganic hybrid particles, and may be resin particles or organic-inorganic hybrid particles. By using these preferable base particles, conductive particles more suitable for electrical connection between the electrodes can be obtained.
  • the conductive particles When connecting the electrodes using the conductive particles, the conductive particles are compressed by placing the conductive particles between the electrodes and then pressing them.
  • the substrate particles are resin particles or organic-inorganic hybrid particles, the conductive particles are easily deformed during the pressure bonding, and the contact area between the conductive particles and the electrode is increased. For this reason, the connection resistance between electrodes becomes still lower.
  • the resin for forming the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; Alkylene terephthalate, polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polysulfone, polyphenylene Oxide, polyacetal, polyimide, polyamideimide, polyether ether Tons, polyethersulfone, and polymers such as obtained by a variety of polymerizable monomer having an ethylene
  • Resin for forming the resin particles can be designed and synthesized, and the hardness of the base particles can be easily controlled within a suitable range, which is suitable for conductive materials and having physical properties at the time of compression.
  • the monomer having the ethylenically unsaturated group may be a non-crosslinkable monomer or a crosslinkable monomer. And a polymer.
  • non-crosslinkable monomer examples include styrene monomers such as styrene and ⁇ -methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( Alkyl (meth) acrylates such as meth) acrylate and isobornyl (meth) acrylate; acids such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate and glycidyl (meth) acrylate Atom
  • crosslinkable monomer examples include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Polyfunctional (meth) acrylates such as acrylate, (poly) tetramethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) cyanure And silane
  • the resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerizing by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.
  • the substrate particles are inorganic particles or organic-inorganic hybrid particles excluding metal particles
  • examples of the inorganic material for forming the substrate particles include silica, alumina, barium titanate, zirconia, and carbon black.
  • the inorganic substance is preferably not a metal.
  • the particles formed by the silica are not particularly limited. For example, after forming a crosslinked polymer particle by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups, firing may be performed as necessary. The particle
  • examples of the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
  • the organic-inorganic hybrid particles are preferably core-shell type organic-inorganic hybrid particles having a core and a shell disposed on the surface of the core.
  • the core is preferably an organic core.
  • the shell is preferably an inorganic shell.
  • the base material particles are preferably organic-inorganic hybrid particles having an organic core and an inorganic shell disposed on the surface of the organic core.
  • Examples of the material for forming the organic core include the resin for forming the resin particles described above.
  • Examples of the material for forming the inorganic shell include inorganic substances for forming the above-described base material particles.
  • the material for forming the inorganic shell is preferably silica.
  • the inorganic shell is preferably formed on the surface of the core by forming a metal alkoxide into a shell-like material by a sol-gel method and then firing the shell-like material.
  • the metal alkoxide is preferably a silane alkoxide.
  • the inorganic shell is preferably formed of a silane alkoxide.
  • the substrate particles are metal particles
  • examples of the metal for forming the metal particles include silver, copper, nickel, silicon, gold, and titanium.
  • the substrate particles are preferably not metal particles.
  • the particle diameter of the substrate particles is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, further preferably 1 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 20 ⁇ m or less, and even more preferably 5 ⁇ m or less. . Particularly preferably, it is 3 ⁇ m or less.
  • the particle diameter of the substrate particles is not less than the above lower limit and not more than the above upper limit, even when the distance between the electrodes is small and the thickness of the conductive portion is increased, small conductive particles can be obtained.
  • the particle diameter of the substrate particles indicates a diameter when the substrate particles are spherical, and indicates a maximum diameter when the substrate particles are not spherical.
  • the said electroconductive particle is equipped with the 1st electroconductive part containing copper as an electroconductive part.
  • the first conductive portion includes not only the case where only copper is used as the metal, but also the case where copper and another metal are used.
  • the copper layer may be a copper alloy layer.
  • metals other than copper in the first conductive part include gold, silver, platinum, zinc, iron, tin, lead, aluminum, cobalt, nickel, indium, palladium, chromium, titanium, antimony, bismuth, thallium, germanium, Examples thereof include cadmium, silicon, tungsten, molybdenum, and tin-doped indium oxide (ITO). As for these metals, only 1 type may be used and 2 or more types may be used together.
  • the first conductive part preferably contains copper as a main metal.
  • the content of copper is preferably 50% by weight or more in 100% by weight of the entire first conductive part.
  • the copper content is preferably 65% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, and particularly preferably 93% by weight or more, in 100% by weight of the entire first conductive part.
  • the copper content is not less than the above lower limit, the flexibility of the conductive particles is appropriately increased, and the connection resistance between the electrodes is further reduced.
  • the thickness of the first conductive portion is preferably 20 nm or more, more preferably 50 nm or more, still more preferably 80 nm or more, preferably 300 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less.
  • the thickness of the first conductive portion is not less than the above lower limit and not more than the above upper limit, the connection resistance is effectively lowered, and corrosion of the conductive portion is further less likely to occur.
  • the Vickers hardness of the first conductive part is preferably 20 or more, more preferably 40 or more. When the Vickers hardness of the first conductive portion is equal to or higher than the lower limit, cracking of the conductive portion is reduced when the pressure is applied, leading to improvement in conduction reliability and connection reliability.
  • the Vickers hardness of the first conductive part is preferably less than 100, more preferably 70 or less. When the Vickers hardness of the first conductive portion is equal to or lower than the above upper limit, cracking of the conductive portion is considerably reduced when pressed, leading to improvement in conduction reliability and connection reliability.
  • the conductive particles include a first conductive part containing copper and a second conductive part containing palladium as a conductive part.
  • the second conductive portion includes not only the case where only palladium is used as the metal but also the case where palladium and another metal are used.
  • the palladium layer may be a palladium alloy layer. It is preferable that the said 2nd electroconductive part is arrange
  • Examples of the metal other than gold in the second conductive part include nickel, gold, silver, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, nickel, indium, chromium, titanium, antimony, bismuth, Examples include thallium, germanium, cadmium, silicon, tungsten, molybdenum, and tin-doped indium oxide (ITO). As for these metals, only 1 type may be used and 2 or more types may be used together.
  • the second conductive part preferably contains palladium as a main metal.
  • the content of palladium is preferably 50% by weight or more in 100% by weight of the entire second conductive part.
  • the content of palladium is preferably 90% by weight or more, more preferably 95% by weight or more, and further preferably 99.9% by weight or more in 100% by weight of the entire second conductive part.
  • the thickness of the second conductive part is preferably 3 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more, preferably 45 nm or less, more preferably 40 nm or less, still more preferably 25 nm or less.
  • the thickness of the second conductive portion is not less than the above lower limit and not more than the above upper limit, the connection resistance is effectively lowered, and corrosion of the conductive portion is further less likely to occur.
  • the second conductive part has a plurality of protrusions on the outer surface.
  • An oxide film is often formed on the surface of the electrode connected by the conductive particles.
  • the oxide particles are effectively eliminated by the protrusions by placing the conductive particles between the electrodes and then pressing them. For this reason, an electrode and electroconductive particle can be made to contact still more reliably, and the connection resistance between electrodes becomes still lower.
  • the conductive particles have an insulating material on the surface, or when the conductive particles are dispersed in the resin and used as a conductive material, the conductive particles and the electrodes are insulated by the protrusions of the conductive particles. Substances or resins are effectively excluded. For this reason, the conduction
  • the number of protrusions on the outer surface of the second conductive portion per one of the conductive particles is preferably 3 or more, more preferably 5 or more, still more preferably 15 or more, and particularly preferably 20 or more.
  • the upper limit of the number of protrusions is not particularly limited. The upper limit of the number of protrusions can be appropriately selected in consideration of the particle diameter of the conductive particles.
  • the average height of the plurality of protrusions is preferably 0.001 ⁇ m or more, more preferably 0.05 ⁇ m or more, preferably 0.9 ⁇ m or less, more preferably 0.2 ⁇ m or less.
  • the connection resistance between the electrodes is effectively reduced.
  • the height of the projection is a virtual line of the conductive portion (dashed line shown in FIG. 1) on the assumption that there is no projection on the line (dashed line L1 shown in FIG. 1) connecting the center of the conductive particles and the tip of the projection.
  • L2 Indicates the distance from the top (on the outer surface of the spherical conductive particles assuming no projection) to the tip of the projection. That is, in FIG. 1, the distance from the intersection of the broken line L1 and the broken line L2 to the tip of the protrusion is shown.
  • a conductive part is formed by electroless plating, and a conductive part is formed by electroless plating on the surface of the base particle. Thereafter, a method of attaching a core substance and further forming a conductive portion by electroless plating can be used.
  • a first conductive part is formed on the surface of the base particle, and then a core substance is disposed on the first conductive part, and then the second conductive part. Examples thereof include a forming method and a method of adding a core substance in the middle of forming a conductive part (first conductive part or second conductive part) on the surface of the base particle.
  • a core substance is added to the dispersion of the base particle, and the core substance is added to the surface of the base particle, for example, van der Waals.
  • examples include a method of accumulating and attaching by force, and a method of adding a core substance to a container containing base particles and attaching the core substance to the surface of the base particles by a mechanical action such as rotation of the container. It is done.
  • the method of making a core substance accumulate and adhere on the surface of the base particle in a dispersion liquid is preferable.
  • the core material is not particularly limited as long as it is different from nickel and the core material has a Mohs hardness of more than 5. When the Mohs hardness is 5 or less, the oxide film does not sufficiently penetrate and the connection resistance tends to increase.
  • the material of the core substance examples include silica (silicon dioxide, Mohs hardness 6-7), titanium oxide (Mohs hardness 7), zirconia (Mohs hardness 8-9), alumina (Mohs hardness 9), tungsten carbide ( And Mohs hardness 9) and diamond (Mohs hardness 10).
  • the material of the core substance is more preferably silica, titanium oxide, zirconia, alumina, tungsten carbide or diamond, further preferably titanium oxide, zirconia, alumina, tungsten carbide or diamond, zirconia, alumina, carbonized. Particularly preferred is tungsten or diamond.
  • the Mohs hardness of the core material is preferably 5.5 or higher, more preferably 6 or higher, still more preferably 7 or higher, and particularly preferably 7.5 or higher.
  • the electrode and the conductive particles are more appropriately in contact with each other, and the connection resistance between the electrodes is further reduced.
  • the shape of the core substance is not particularly limited.
  • the shape of the core substance is preferably a lump.
  • Examples of the core substance include a particulate lump, an agglomerate in which a plurality of fine particles are aggregated, and an irregular lump.
  • the average diameter (average particle diameter) of the core substance is preferably 20 nm or more, more preferably 50 nm or more, still more preferably 100 nm or more, preferably 1000 nm or less, more preferably 600 nm or less, still more preferably 500 ⁇ m or less, particularly Preferably it is 250 nm or less.
  • the connection resistance between the electrodes is effectively reduced.
  • the connection resistance is effectively lowered, and corrosion of the conductive part is further less likely to occur.
  • the “average diameter (average particle diameter)” of the core substance indicates a number average diameter (number average particle diameter).
  • the average diameter of the core material is obtained by observing 50 arbitrary core materials with an electron microscope or an optical microscope and calculating an average value.
  • Ratio of the total thickness of the first conductive portion and the second conductive portion to the average diameter of the core material Is preferably 0.1 or more, more preferably 0.3 or more, preferably 6 or less, more preferably 5 or less, and still more preferably 2 or less.
  • the ratio is not less than the lower limit and not more than the upper limit, the connection resistance is effectively reduced, Corrosion is less likely to occur.
  • the conductive particles according to the present invention preferably include an insulating material disposed on the outer surface of the second conductive portion.
  • an insulating material disposed on the outer surface of the second conductive portion.
  • an insulating material is present between the plurality of electrodes, so that it is possible to prevent a short circuit between electrodes adjacent in the lateral direction instead of between the upper and lower electrodes.
  • the insulating particles between the conductive portions of the conductive particles and the electrodes can be easily removed by pressurizing the conductive particles with the two electrodes.
  • the insulating material is an insulating particle because the insulating material can be more easily removed when the electrodes are crimped.
  • thermoplastic resin examples include vinyl polymers and vinyl copolymers.
  • thermosetting resin an epoxy resin, a phenol resin, a melamine resin, etc.
  • water-soluble resin examples include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinyl pyrrolidone, polyethylene oxide, and methyl cellulose. Of these, water-soluble resins are preferable, and polyvinyl alcohol is more preferable.
  • the outer surface of the second conductive part and the surface of the insulating particles may each be coated with a compound having a reactive functional group.
  • the outer surface of the second conductive part and the surface of the insulating particles may not be directly chemically bonded, but may be indirectly chemically bonded by a compound having a reactive functional group.
  • the carboxyl group may be chemically bonded to a functional group on the surface of the insulating particle through a polymer electrolyte such as polyethyleneimine.
  • the average diameter (average particle diameter) of the insulating material can be appropriately selected depending on the particle diameter of the conductive particles and the use of the conductive particles.
  • the average diameter (average particle diameter) of the insulating material is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less.
  • the average diameter of the insulating material is not less than the above lower limit, the conductive layers of the plurality of conductive particles are difficult to contact when the conductive particles are dispersed in the binder resin.
  • the average diameter of the insulating particles is not more than the above upper limit, it is not necessary to make the pressure too high in order to eliminate the insulating material between the electrodes and the conductive particles when the electrodes are connected. There is no need for heating.
  • the “average diameter (average particle diameter)” of the insulating material indicates a number average diameter (number average particle diameter).
  • the average diameter of the insulating material is obtained using a particle size distribution measuring device or the like.
  • the antioxidant is not particularly limited.
  • examples of the antioxidant include nitrogen-containing compounds.
  • the nitrogen-containing compound include benzotriazole compounds, imidazole compounds, thiazole compounds, triazines, 2-mercaptopyrimidine, indole, pyrrole, adenine, thiobarbituric acid, thiouracil, rhodanine, thiozolidinethione, 1-phenyl-2-tetrazoline- Examples include 5-thione and 2-mercaptopyridine.
  • the said antioxidant only 1 type may be used and 2 or more types may be used together.
  • benzotriazole compounds include benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-methyl-1H-benzotriazole, 5,6-dimethyl-1H-benzotriazole, and benzotriazole. A butyl ester etc. are mentioned.
  • the imidazole compound include imidazole and benzimidazole.
  • the thiazole compound include thiazole or benzothiazole.
  • the conductive material according to the present invention includes the conductive particles described above and a binder resin.
  • the conductive particles are preferably used by being dispersed in a binder resin, and are preferably used as a conductive material by being dispersed in a binder resin.
  • the conductive material is preferably an anisotropic conductive material.
  • the conductive material is preferably used for electrical connection between electrodes.
  • the conductive material is preferably a conductive material for circuit connection.
  • the binder resin is not particularly limited.
  • As the binder resin a known insulating resin is used.
  • the binder resin preferably contains a thermoplastic component (thermoplastic compound) or a curable component, and more preferably contains a curable component.
  • the curable component include a photocurable component and a thermosetting component. It is preferable that the said photocurable component contains a photocurable compound and a photoinitiator.
  • the thermosetting component preferably contains a thermosetting compound and a thermosetting agent.
  • the binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. As for the said binder resin, only 1 type may be used and 2 or more types may be used together.
  • Examples of the vinyl resin include vinyl acetate resin, acrylic resin, and styrene resin.
  • examples of the thermoplastic resin include polyolefin resin, ethylene-vinyl acetate copolymer, and polyamide resin.
  • examples of the curable resin include an epoxy resin, a urethane resin, a polyimide resin, and an unsaturated polyester resin.
  • the curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin.
  • the curable resin may be used in combination with a curing agent.
  • thermoplastic block copolymer examples include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated product of a styrene-butadiene-styrene block copolymer, and a styrene-isoprene. -Hydrogenated products of styrene block copolymers.
  • the elastomer examples include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
  • the conductive material includes, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, and a light stabilizer.
  • a filler for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, and a light stabilizer.
  • Various additives such as an agent, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant may be contained.
  • the conductive material according to the present invention can be used as a conductive paste and a conductive film.
  • the conductive material according to the present invention is a conductive film
  • a film that does not include conductive particles may be laminated on a conductive film that includes conductive particles.
  • the conductive paste is preferably an anisotropic conductive paste.
  • the conductive film is preferably an anisotropic conductive film.
  • the content of the binder resin in 100% by weight of the conductive material is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, preferably It is 99.99 weight% or less, More preferably, it is 99.9 weight% or less.
  • the content of the binder resin is not less than the above lower limit and not more than the above upper limit, the conductive particles are efficiently arranged between the electrodes, and the connection reliability of the connection target member connected by the conductive material is further increased.
  • the content of the conductive particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 80% by weight or less, more preferably 60% by weight. Hereinafter, it is more preferably 40% by weight or less, particularly preferably 20% by weight or less, and most preferably 10% by weight or less.
  • the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conduction reliability between the electrodes is further enhanced.
  • connection structure can be obtained by connecting the connection object members using the conductive particles or using a conductive material containing the conductive particles and a binder resin.
  • connection structure includes a first connection target member, a second connection target member, and a connection part connecting the first and second connection target members, and the material of the connection part has been described above.
  • the connection structure is preferably a conductive particle or a conductive material including the above-described conductive particles and a binder resin. It is preferable that the connection portion is formed of the above-described conductive particles or a conductive material containing the above-described conductive particles and a binder resin. In the case where conductive particles are used, the connection portion itself is conductive particles. That is, the first and second connection target members are connected by the conductive particles.
  • FIG. 3 is a cross-sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention.
  • a connection structure 51 shown in FIG. 3 includes a first connection target member 52, a second connection target member 53, and a connection portion 54 connecting the first and second connection target members 52 and 53.
  • the connection part 54 is formed of a conductive material including the conductive particles 1. It is preferable that the conductive material has thermosetting properties and the connection portion 54 is formed by thermosetting the conductive material. It is preferable that the connection part 54 is a thermosetting material of a conductive material.
  • the conductive particles 1 are schematically shown for convenience of illustration. Instead of the conductive particles 1, conductive particles 1A or the like may be used.
  • the first connection target member 52 has a plurality of first electrodes 52a on the surface (upper surface).
  • the second connection target member 53 has a plurality of second electrodes 53a on the surface (lower surface).
  • the first electrode 52 a and the second electrode 53 a are electrically connected by one or a plurality of conductive particles 1. Therefore, the first and second connection target members 52 and 53 are electrically connected by the conductive particles 1.
  • the manufacturing method of the connection structure is not particularly limited.
  • the conductive material is disposed between the first connection target member and the second connection target member to obtain a laminate, and then the laminate is heated and pressurized. Methods and the like.
  • the pressurizing pressure is about 9.8 ⁇ 10 4 to 4.9 ⁇ 10 6 Pa.
  • the heating temperature is about 120 to 220 ° C.
  • connection target member examples include electronic components such as semiconductor chips, capacitors, and diodes, and electronic components such as printed boards, flexible printed boards, glass epoxy boards, and glass boards.
  • the connection target member is preferably an electronic component.
  • the conductive particles are preferably used for electrical connection of electrodes in an electronic component.
  • the electrode provided on the connection target member examples include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a silver electrode, a copper electrode, a molybdenum electrode, and a tungsten electrode.
  • the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode.
  • the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode.
  • the electrode formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated
  • the material for the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element.
  • the trivalent metal element include Sn, Al, and Ga.
  • Example 1 Adhering Step of Core Material Divinylbenzene copolymer resin particles having a particle size of 3.0 ⁇ m (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) were prepared as base material particles A.
  • the substrate particles A were etched and washed with water. Next, the base particle A was added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
  • the base particle A to which palladium was adhered was stirred and dispersed in 300 mL of ion exchange water for 3 minutes to obtain a dispersion.
  • 1 g of alumina particle slurry (average particle diameter 150 nm, Mohs hardness 9) was added to the dispersion over 3 minutes to obtain a suspension of substrate particles A to which the core material was adhered.
  • Copper layer forming step Copper sulfate (pentahydrate) 40 g / L, ethylenediaminetetraacetic acid (EDTA) 100 g / L, sodium gluconate 50 g / L, formaldehyde 25 g / L, and pH 10
  • EDTA ethylenediaminetetraacetic acid
  • the electroless plating solution was gradually added to the suspension of the base particle A, and electroless copper plating was performed while stirring at 50 ° C. Thus, copper plating particles having a copper layer provided on the surface were obtained. The thickness of the copper layer was 125 nm.
  • Palladium layer forming step 10 g of the obtained copper plating particles were dispersed in 500 mL of ion-exchanged water using an ultrasonic processor to obtain a particle suspension.
  • the electroless plating solution was gradually added to perform electroless palladium plating.
  • the amount of electroless plating solution added was adjusted so that the thickness of the palladium layer was 100 nm.
  • the obtained palladium-plated resin particles were washed with distilled water and methanol and then vacuum-dried.
  • the electroconductive particle by which the copper layer was provided in the surface of the resin particle and the palladium layer was provided in the surface of the copper layer was obtained.
  • the thickness of the palladium layer was 25 nm.
  • Example 2 Conductive particles were obtained in the same manner as in Example 1 except that the alumina particles were changed to titanium dioxide particles (average particle diameter 150 nm, Mohs hardness 7).
  • Example 3 Conductive particles were obtained in the same manner as in Example 1 except that the alumina particles were changed to tungsten carbide particles (average particle diameter 150 nm, Mohs hardness 9).
  • Example 4 The particles obtained in Example 1 were subjected to rust prevention treatment to obtain conductive particles. Benzotriazole was used as a rust inhibitor.
  • Example 5 Conductive particles were obtained in the same manner as Example 4. Using the obtained conductive particles, an adhesion process of insulating particles was performed.
  • the insulating particles were dispersed in ion exchange water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating particles.
  • Conductive particles 10 g obtained by the same manner as in Example 4 to which insulating particles were not attached were dispersed in 500 mL of ion-exchanged water, 4 g of an aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 6 hours. After filtration through a 3 ⁇ m mesh filter, the particles were further washed with methanol and dried to obtain conductive particles having insulating particles attached thereto.
  • Example 6 to 19 The particle diameter of the base particle, the type of core substance, the Mohs hardness and average diameter of the material, the main metal of the first conductive part (copper layer), the Cu content, the thickness and the Vickers hardness, and the second conductivity The content and thickness of the main metal of the part (palladium layer), Pd, presence / absence of an insulating material, presence / absence of rust prevention treatment, and the number of protrusions in the conductive particles were set as shown in Table 1 below. Except for the above, conductive particles of Examples 6 to 19 were obtained in the same manner as Example 1.
  • a transparent glass substrate having an ITO electrode pattern with an L / S of 20 ⁇ m / 20 ⁇ m on the upper surface was prepared. Further, a semiconductor chip having a gold electrode pattern with L / S of 20 ⁇ m / 20 ⁇ m on the lower surface was prepared.
  • the anisotropic conductive paste immediately after production was applied to a thickness of 30 ⁇ m to form an anisotropic conductive paste layer.
  • the semiconductor chip was stacked on the anisotropic conductive paste layer so that the electrodes face each other.
  • a pressure heating head is placed on the upper surface of the semiconductor chip and a pressure of 1 MPa is applied to form the anisotropic conductive paste layer. It hardened
  • Connection resistance is 2.0 ⁇ or less ⁇ : Connection resistance exceeds 2.0 ⁇ , 3.0 ⁇ or less ⁇ : Connection resistance exceeds 3.0 ⁇ , 5.0 ⁇ or less ⁇ : Connection resistance exceeds 5.0 ⁇
  • connection resistance after reliability test (conduction reliability) The connection structure obtained by the above (2) evaluation of the initial connection resistance was left under the conditions of 85 ° C. and relative humidity of 85%. 150 hours after the start of standing, the connection resistance between the electrodes was measured by the 4-terminal method in the same manner as in the above (2) evaluation of the initial connection resistance. The connection resistance after the reliability test was determined according to the following criteria.
  • the obtained resin composition was applied to a 50 ⁇ m-thick PET (polyethylene terephthalate) film whose one surface was release-treated, and dried with hot air at 70 ° C. for 5 minutes to produce an anisotropic conductive film.
  • the thickness of the obtained anisotropic conductive film was 12 ⁇ m.
  • the obtained anisotropic conductive film was cut into a size of 5 mm ⁇ 5 mm.
  • a two-layer flexible printed board width: 2 cm, length: 1 cm) having a Ni base Au electrode was bonded after being aligned so that the electrodes overlap each other.
  • the laminated body of the glass substrate and the two-layer flexible printed circuit board was thermocompression bonded under pressure bonding conditions of 10 N, 180 ° C., and 20 seconds to obtain a connection structure.
  • a two-layer flexible printed board in which a Ni base and Au are sequentially formed on a polyimide film was used.
  • Counting the number of particles with plating cracks In the connection part of the obtained connection structure, the number of conductive particles in which plating cracks in 1000 conductive particles were confirmed was counted.
  • the plating crack was determined according to the following criteria.
  • connection resistance after the above (3) reliability test the obtained connection structure was left under conditions of 85 ° C. and relative humidity 85%. Even after obtaining the connection structure after leaving the conductive particles before obtaining the connection structure under the conditions of 85 ° C. and 85% relative humidity, the above-mentioned (3) after the reliability test The same tendency as the evaluation result of the connection resistance was observed.
  • connection resistance after (3) reliability test between Example 7 and Example 13 the amount of change in connection resistance in Example 7 is smaller than that in Example 13 and the conduction reliability is excellent. It was. This result is mainly influenced by the ratio (the total thickness of the first conductive portion and the second conductive portion / the average diameter of the core substance).
  • Example 1 was lower in connection resistance and superior in conductivity than Example 10.
  • the amount of change in connection resistance is smaller in Example 1 than in Example 10, and the conduction reliability is increased. It was excellent.
  • Example 8 had a lower connection resistance and superior conductivity than Example 9.
  • the change in connection resistance in Example 8 is smaller than that in Example 9 and conduction reliability is improved. It was excellent.
  • Example 8 Regarding the evaluation results of the connection resistance after (3) reliability test between Example 1 and Example 8, the amount of change in connection resistance is smaller in Example 1 than in Example 8, and the conduction reliability is excellent. It was. Regarding the evaluation results of (2) initial connection resistance between Example 8 and Example 12, Example 8 had a lower connection resistance than Example 12 and was excellent in conductivity. In addition, with regard to the evaluation results of the connection resistance after (3) reliability test between Example 8 and Example 12, Example 8 has a smaller amount of change in connection resistance than that of Example 12, and the conduction reliability. It was excellent. These results are mainly influenced by the average diameter of the core material.
  • Example 1 was lower in connection resistance and superior in conductivity than Example 6.
  • the amount of change in connection resistance in Example 1 is smaller than that in Example 6 and conduction reliability is improved. It was excellent.
  • Example 6 was lower in connection resistance than Example 7 and excellent in conductivity.
  • the amount of change in connection resistance is smaller in Example 6 than in Example 7, and the conduction reliability is increased. It was excellent.
  • the amount of change in connection resistance in Example 7 is smaller than that in Example 13 and the conduction reliability is excellent. It was.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Conductive Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Non-Insulated Conductors (AREA)
PCT/JP2015/079816 2014-10-22 2015-10-22 導電性粒子、導電材料及び接続構造体 WO2016063941A1 (ja)

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KR20210083246A (ko) 2018-11-07 2021-07-06 니폰 가가쿠 고교 가부시키가이샤 피복 입자 및 그것을 함유하는 도전성 재료, 그리고 피복 입자의 제조 방법

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KR102598343B1 (ko) 2020-10-06 2023-11-06 덕산네오룩스 주식회사 도전입자, 도전재료 및 접속 구조체
CN113299892B (zh) * 2021-05-21 2022-06-28 葫芦岛市铭浩新能源材料有限公司 一种铁掺杂的二氧化钛/碳化钨锂离子电池负极材料的制备方法

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