WO2012118061A1 - Composition conductrice de l'électricité - Google Patents

Composition conductrice de l'électricité Download PDF

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Publication number
WO2012118061A1
WO2012118061A1 PCT/JP2012/054882 JP2012054882W WO2012118061A1 WO 2012118061 A1 WO2012118061 A1 WO 2012118061A1 JP 2012054882 W JP2012054882 W JP 2012054882W WO 2012118061 A1 WO2012118061 A1 WO 2012118061A1
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Prior art keywords
silver
conductive composition
component
particles
coated
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PCT/JP2012/054882
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English (en)
Japanese (ja)
Inventor
宜司 水村
陽子 長柄
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ナミックス株式会社
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Priority to KR1020137025349A priority Critical patent/KR101971746B1/ko
Priority to CN201280010616.6A priority patent/CN103391973B/zh
Priority to JP2013502355A priority patent/JP5927177B2/ja
Publication of WO2012118061A1 publication Critical patent/WO2012118061A1/fr

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers

Definitions

  • the present invention relates to a conductive composition useful as a circuit pattern formation or die bonding agent.
  • conductive compositions are used as bonding materials for forming circuit patterns and bonding semiconductor elements such as ICs and LSIs to lead frames or substrates.
  • the conductive circuit can be formed by applying a conductive composition on a substrate by screen printing or the like and then thermally curing the conductive composition.
  • the bonding between the semiconductor element and the lead frame or the substrate can be performed by applying a conductive composition to a predetermined part of the lead frame or the substrate, mounting the semiconductor element, and thermally curing the semiconductor element.
  • a conductive composition is one that develops conductivity by blending silver particles, but in recent years, while blending cheaper nickel particles and silver plating particles, it also has adhesiveness and conductivity.
  • an electrically conductive composition that can provide a cured film.
  • conductive compositions containing silver-coated particles have been proposed (see Patent Documents 1 to 3).
  • the conductive composition of Patent Document 1 requires the use of an organometallic complex containing titanium and / or zirconium, and cannot sufficiently contribute to cost reduction.
  • the conductive compositions of Patent Documents 2 and 3 use a thermoplastic resin such as a polyester resin having a molecular weight of 3000 or more and / or a modified polyester resin, and soften at a high temperature (260 ° C.). In addition, it becomes difficult to maintain reliability in reflow after moisture absorption.
  • flake powder having an average particle size / thickness of 2 or more and a high degree of flaming when used for bonding a chip and a substrate, a plurality of flakes overlap to obtain vertical conduction, and consequently The contact resistance is high, and unlike silver, electricity passes through the periphery of the core material, so the conduction path is long, and the resistance value of vertical conduction is generally high. Furthermore, flake powder having a high average particle size / thickness of 2 or more and having a high degree of flaming has a large specific surface area. In order to uniformly coat with silver, it is necessary to increase the coating rate of silver, thus reducing the cost effectively. It will not be expected.
  • This invention is made
  • the conductive composition is a flaky silver having a specific shape selected from the group consisting of silver-coated ceramic particles, silver-coated glass particles, and silver-coated aluminum particles. It has been discovered that blending the coated particles results in a cured film that is sufficient in terms of adhesion and conductivity, thus completing the present invention. In the present invention, since relatively inexpensive silver-coated particles are used, the cost can be reduced at the same time.
  • a volume average particle diameter D50 selected from the group consisting of silver-coated ceramic particles, silver-coated glass particles, and silver-coated aluminum particles and measured by a laser light scattering method is 1 to 10 ⁇ m, and a scanning electron microscope Flaky silver-coated particles having an average thickness T measured by observation of 0.3 to 10 ⁇ m and an aspect ratio T / D50 of 0.3 to 1.0
  • B thermosetting resin
  • C It relates to a conductive composition containing a curing agent.
  • a conductive composition that satisfies both cost reduction and good adhesion and expression of conductivity.
  • the conductive composition of the present invention is selected from the group consisting of (A) silver-coated ceramic particles, silver-coated glass particles, and silver-coated aluminum particles, and has a volume average particle diameter D50 measured by a laser light scattering method of 1 Including flaky silver-coated particles having an average thickness T measured by observation with a scanning electron microscope of 0.3 to 10 ⁇ m and an aspect ratio T / D50 of 0.3 to 1.0 .
  • the flaky silver-coated particles of the component (A) may be used alone or in combination of two or more.
  • the core of the flaky silver-coated particles of component (A) is made of ceramic, glass or aluminum.
  • ceramics include alumina, silicon carbide, silicon nitride, barium titanate, boron nitride, ferrite, steatite, zinc oxide, and zirconia. Freedom to obtain, freedom to control particle size and shape, and cost In particular, alumina is preferable.
  • the flaky silver-coated particles of the component have a volume average particle diameter D50 of 1 to 10 ⁇ m as measured by a laser light scattering method.
  • D50 volume average particle diameter
  • the workability of the conductive composition is good.
  • the film thickness of the conductive composition is often set to 20 to 30 ⁇ m, but the film thickness increases due to the presence of the component (A) and the chip is tilted. This can also be avoided.
  • D50 is a glass-coated particle with 2 cups of microspatella, taken in a 300 ml beaker, put 50 ml of 0.5% sodium sulfosuccinate dioctyl ester solution, and dispersed with an ultrasonic homogenizer for 10 minutes. (A Coulter LS230 (manufactured by Beckman Coulter)) The average value of 50% cumulative diameter is D50.
  • D50 of the flaky silver-coated particles of the component (A) is 1 to 10 ⁇ m, preferably 3 to 8 ⁇ m.
  • the flaky silver-coated particles of the component (A) have an average thickness T measured by observation with a scanning electron microscope of 0.3 to 10 ⁇ m.
  • T is in this range, the workability of the conductive composition is good, and it is also possible to avoid the inconvenience that the chip is inclined due to the component (A) in joining the semiconductor chip and the substrate.
  • the average thickness is 2 g of silver-coated particles, 5 g of epoxy resin (Epoxy Resin 20-8130-032 (manufactured by BUEHLER)) and 1 g of epoxy resin curing agent (EPOXY HARDENER 20-8132-008 (manufactured by BUEHLER)) in a 25 mm diameter clear cup.
  • T of the flaky silver-coated particles of the component (A) is 0.3 to 10 ⁇ m, preferably 1 to 8 ⁇ m.
  • the flaky silver-coated particles of the component have an aspect ratio T / D50 of 0.3 to 1.0.
  • T / D50 aspect ratio of 0.3 to 1.0.
  • the semiconductor chip and the substrate are more conductive than the one having a higher degree of fragmentation (that is, the T / D50 is less than 0.3).
  • the number of silver-coated particles can be reduced, thereby making it possible to reduce the contact resistance between the silver-coated particles.
  • the one with a high degree of fragmentation has a long conduction path because electricity passes around the core material, whereas the silver-coated fine particles of the present invention require a short conduction path, thereby reducing the resistance value of vertical conduction. Is possible.
  • T / D50 is preferably 0.3 to 1.0, and more preferably 0.4 to 1.0.
  • the flaky silver-coated particles of component (A) have a maximum particle size of 40 ⁇ m from the viewpoint of workability (especially suppression of nozzle clogging during dispensing) and prevention of tip tilting in bonding between the semiconductor chip and the substrate.
  • the maximum particle size is a value measured with a light scattering analysis type particle size distribution measuring device.
  • the maximum particle size is more preferably 35 ⁇ m or less, and further preferably 30 ⁇ m or less.
  • the silver coating layer is preferably 10 to 60% by mass of the total weight of the silver-coated particles, more preferably, from the viewpoint of silver coverage on the core material and conductivity. Is 20 to 50% by mass, more preferably 20 to 40% by mass.
  • the weight of the silver coating layer can be calculated from the weight of the silver coating particles and the core material measured by dissolving the silver coating layer in nitric acid and removing silver.
  • the flaky silver-coated particles of the component (A) are preferably provided with a uniform silver coating layer, the silver coating layer is thick, and the specific gravity of the entire particle, and hence the specific gravity of the conductive composition, is increased.
  • the thickness of the silver coating layer is preferably 50 to 300 nm from the viewpoint of avoiding a decrease in efficiency by reducing the volume when the conductive composition is applied with the same weight and obtaining stable conductivity. is there.
  • the thickness of the silver coating layer is more preferably 50 to 200 nm, still more preferably 80 to 200 nm, and particularly preferably 80 to 150 nm.
  • the thickness of the silver coating layer can be measured by preparing a sample having the same thickness as the average thickness T, and using a field emission scanning electron microscope (JSM-7500F manufactured by JEOL) at a magnification of 10,000 to 30,000 times.
  • the flaky silver-coated particles of the component can be obtained by coating the ceramic, glass, and aluminum particles serving as the core with silver by a method such as electroless plating, sputtering, or vapor deposition.
  • the flaky silver-coated particles of the component (A) are preferably those that have been surface-treated with a fatty acid, a salt thereof, or a coupling agent from the viewpoint of stability when formed into a paste.
  • fatty acids examples include propionic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, acrylic acid, oleic acid, linoleic acid, arachidonic acid, epoxy resin, phenolic resin, acrylate resin, From the viewpoint of compatibility with isocyanate resin and maleimide resin, wettability, and reactivity to resin, oleic acid and stearic acid are preferred.
  • fatty acid salts include metal salts of the above fatty acids such as lithium, sodium, potassium, barium, magnesium, calcium, aluminum, iron, cobalt, manganese, lead, zinc, tin, strontium, zirconium, silver, copper, and epoxy. From the viewpoint of compatibility with resins, phenolic resins, acrylate resins, isocyanate resins, and maleimide resins, wettability, and reactivity to resins, sodium salts are preferred.
  • Examples of the surface treatment method using a fatty acid or a fatty acid salt include a method in which the fatty acid or the fatty acid salt is dissolved in an optionally heated alcohol, and silver-coated particles are added thereto, followed by stirring for a certain time.
  • Examples of coupling agents include silane coupling agents, titanate coupling agents, aluminum coupling agents, etc., compatibility with epoxy resins, phenol resins, acrylate resins, isocyanate resins, maleimide resins, wettability, resins From the viewpoint of reactivity to silane, a silane coupling agent and a titanate coupling agent are preferable.
  • a surface treatment method using a coupling agent a method in which silver-coated particles are sprayed onto an agitator where the particles are being agitated, the coupling agent is dissolved in alcohol, and silver-coated particles are added thereto and stirred. There is a method of performing and processing.
  • the conductive composition of the present invention contains (B) a thermosetting resin.
  • a thermosetting resin of a component is not specifically limited, For example, an epoxy resin, an acrylic resin, a silicone resin, a urethane resin, a maleimide resin etc. are mentioned.
  • a thermosetting resin may be individual or may use multiple types together.
  • the thermosetting resin of component (B) is preferably an epoxy resin from the viewpoints of adhesiveness, curability and heat resistance required for the die bonding agent.
  • the epoxy resin is preferably liquid at normal temperature, but even if it is solid at normal temperature, it can be diluted with another liquid epoxy resin or diluent and used in liquid form.
  • Specific examples of epoxy resins include bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, novolac type epoxy resins, alicyclic epoxy resins, and naphthalene type epoxy resins.
  • Ether-based or polyether-based epoxy resins for example, polyoxypropylene-modified epoxy resins such as polyoxypropylene bisphenol A diglycidyl ether), oxirane ring-containing polybutadiene, diglycidyl esterified modified products of dimer acid with epichlorohydrin, epoxy groups A polybutadiene compound having a molecular weight, a silicone epoxy copolymer resin, an aminophenol type epoxy resin (for example, N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropylene) Piruokishi) aniline), and the like.
  • polyoxypropylene-modified epoxy resins such as polyoxypropylene bisphenol A diglycidyl ether
  • oxirane ring-containing polybutadiene diglycidyl esterified modified products of dimer acid with epichlorohydrin
  • epoxy groups A polybutadiene compound having a molecular weight a silicone epoxy copolymer resin
  • the liquid epoxy resin includes a bisphenol A type epoxy resin having an average molecular weight of about 400 or less; a branched polyfunctional bisphenol A type epoxy resin such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; Bisphenol F type epoxy resin; phenol novolak type epoxy resin having an average molecular weight of about 570 or less; vinyl (3,4-cyclohexene) dioxide, 3,4-epoxycyclohexylcarboxylic acid (3,4-epoxycyclohexyl) methyl, adipine Cycloaliphatic epoxies such as bis (3,4-epoxy-6-methylcyclohexylmethyl) acid, 2- (3,4-epoxycyclohexyl) 5,1-spiro (3,4-epoxycyclohexyl) -m-dioxane Resin; 3,3 ' Biphenyl type epoxy resin such as 5,5′-tetra
  • An epoxy resin having a silicone skeleton such as 1,3-bis (3-glycidoxypropyl) -1,1,3,3-tetramethyldisiloxane can also be used.
  • the epoxy resin can be used in combination with a solid or ultra-high viscosity epoxy resin at room temperature, and as such an epoxy resin, a high molecular weight bisphenol A type epoxy resin, a novolac epoxy resin, a tetrabromobisphenol A type epoxy resin. And dicyclopentadiene type epoxy resin, isocyanate-modified epoxy resin, fluorene type epoxy resin, biphenyl aralkyl epoxy resin and the like. These can be used in combination with an epoxy resin and / or a diluent that is liquid at room temperature to adjust fluidity.
  • low-viscosity epoxy resins such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butanediol glycidyl ether, neopentyl glycol diester Glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,6-hexanediol diglycidyl ether, p-tert-butylphenylglycidyl ether, dicyclopentadiene dimethanol diglycidyl ether, glycidyl ether of trimethylolpropane Diglycidyl ether of polytetramethylene ether glycol, diglycidyl ether of dimer acid and diglycidyl ether of polypropylene glycol, glycerine jig Glycidyl ether,
  • acrylic resins examples include neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane dimethacrylate, and trimethylolpropane triacrylate.
  • silicone resins include epoxy-modified polysiloxane, alicyclic epoxy-modified polysiloxane, carbinol-modified polysiloxane, carboxyl-modified polysiloxane, monoamine-modified polysiloxane, diamine-modified polysiloxane, hydrogen-modified polysiloxane, mercapto-modified polysiloxane, Examples include methacryl-modified polysiloxane and diol-modified polysiloxane.
  • urethane resin examples include isocyanate resins, isocyanate resins whose isocyanate groups are blocked with ⁇ -caprolactam, epoxy-modified urethane resins, methacrylate-modified urethane resins, and acrylate-modified urethane resins.
  • maleimide resins include bismaleimide resins (4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A type diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl 4,4′-diphenylmethane).
  • Bismaleimide 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide- (2,2,4-trimethyl) hexane), monomaleimide resin (N-phenylmaleimide, N-cyclohexylmaleimide, o- Methylphenylmaleimide, p-hydroxyphenylmaleimide, p-carboxyphenylmaleimide, N-dodecylmaleimide).
  • the conductive composition of the present invention contains (C) a curing agent.
  • curing agent can be suitably selected with a combination with a thermosetting resin, for example, a phenol resin, an amine compound, an acid anhydride, a peroxide, a metal complex, an azo compound etc. are mentioned.
  • curing agent may be individual or may use multiple types together.
  • phenol resin examples include bisphenol F type phenol resin, allyl phenol resin, phenol novolac resin, cresol novolac resin, naphthol modified phenol resin, dicyclopentadiene modified phenol resin, p-xylene modified phenol resin and the like.
  • amine compounds include aliphatic polyamines, aromatic amines, modified polyamines (eg, polyaminoamides, polyaminoimides, polyaminoesters, polyaminoureas, polyether-modified amines), tertiary amine compounds, and imidazole compounds (eg, 2 -Methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2,2-diamino- 6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, etc.), hydrazide compounds, dicyanamide compounds, melamine compounds and the like.
  • modified polyamines eg, polyaminoamides, polyaminoimides, polyaminoesters, polyaminoureas, poly
  • acid anhydrides include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylheimic acid anhydride, and alkenyl-substituted succinic acid.
  • acid anhydride methyl nadic acid anhydride, glutaric acid anhydride and the like.
  • 2,4-diethylpentanedioic anhydride 3,4-dimethyl-6- (2-methyl-1-propenyl) -1,2,3,6-tetrahydrophthalic anhydride
  • Peroxides include 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanate, t-butylperoxybenzoate, t-butylperoxyneodecanoate, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, t-butylperoxybenzoate, dicumyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, di (2- t-butylperoxyisopropyl) benzene, 2,2-di (4,4-di- (butylperoxy) cyclohexyl) propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3 -Tetramethylbutyl hydroperoxide, cumene hydroperoxide, Examples include 1,1-di (t-butylperoxy) cycl
  • metal complex examples include alkyl acetoacetate aluminum diisopropylate, aluminum tris (acetylacetonate), aluminum acrylate, aluminum bisethylacetoacetate diisopropylate, and magnesium 2-ethylhexanoate.
  • conductive particles other than the component (A) may be blended.
  • the total amount of the conductive particles other than the component (A) is preferably 50% by mass or less, more preferably 30% in total in all the conductive particles (the silver-coated particles of the component (A) and the conductive particles other than the component (A)). Most preferably, only the silver-coated particles of component (A) are used as the conductive particles.
  • spherical silver-coated ceramic particles, silver-coated glass particles, and silver-coated aluminum particles can be used as the conductive particles.
  • the core of the spherical silver-coated particles is preferably made of ceramic, glass or aluminum.
  • Ceramics include alumina, silicon carbide, silicon nitride, barium titanate, boron nitride, ferrite, steatite, zinc oxide, and zirconia. Freedom to obtain, freedom to control particle size and shape, and cost From this point, alumina is particularly preferable.
  • the spherical silver-coated particles preferably have a volume average particle diameter D50 measured by a laser light scattering method of 1 to 20 ⁇ m, more preferably 2 to 15 ⁇ m.
  • the spherical silver-coated particles are preferably 10 to 50% by mass, more preferably, of the total weight of the silver-coated particles having a spherical silver coating layer, from the viewpoint of silver coverage on the core material and conductivity.
  • Spherical silver-coated particles preferably have a uniform silver coating layer, and the thickness of the silver coating layer increases, and the specific gravity of the entire particle, and hence the specific gravity of the conductive composition, increases.
  • the thickness is preferably 50 to 300 nm from the viewpoint of avoiding a decrease in efficiency due to a decrease in volume when an object is coated with the same weight and obtaining stable conductivity.
  • the thickness of the silver coating layer is more preferably 50 to 200 nm, still more preferably 70 to 150 nm.
  • conductive particles other than the component (A) silver particles, copper particles, nickel particles, palladium particles, indium particles, tin particles, zinc particles, bismuth particles, or alloys thereof can also be used.
  • the shape is not particularly limited.
  • a solvent may be added to the conductive composition of the present invention.
  • the solvent is not particularly limited, and examples thereof include alcohol solvents such as ethylene glycol, propylene glycol, dihydroterpineol; toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, p-cymene, tetralin, and petroleum aromatic hydrocarbons.
  • Aromatic hydrocarbon solvents such as mixtures; terpene alcohols such as terpineol, linalool, geraniol, citronellol; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n- Butyl ether, propylene glycol mono-tert-butyl ether, diethylene glycol monoethyl ether, die Ether alcohol solvents such as ethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether; ketone solvents such as methyl isobutyl ketone; and ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Examples thereof include ester solvents such as acetate, ethylene glycol monobutyl ether a
  • the conductive composition of the present invention includes an inorganic filler (for example, fumed silica, calcium carbonate, talc, etc.) and a coupling agent (for example, ⁇ -glycol) within the range that does not impair the predetermined effects of the present invention.
  • an inorganic filler for example, fumed silica, calcium carbonate, talc, etc.
  • a coupling agent for example, ⁇ -glycol
  • Silane coupling agents such as Sidoxypropyltrimethoxysilane, Titanate coupling agents such as Tetraoctylbis (ditridecylphosphite) titanate), Silane monomers (eg, tris (3- (trimethoxysilyl) propyl) isocyanurate ), Plasticizer (for example, copolymer such as carboxyl group-terminated polybutadiene-acrylonitrile, silicone rubber, silicone rubber powder, silicone resin powder, resin powder such as acrylic resin powder), flame retardant, antioxidant, antifoaming agent, etc. can do.
  • Plasticizer for example, copolymer such as carboxyl group-terminated polybutadiene-acrylonitrile, silicone rubber, silicone rubber powder, silicone resin powder, resin powder such as acrylic resin powder
  • flame retardant antioxidant, antifoaming agent, etc.
  • the conductive composition of the present invention is composed of (A) component, (B) component and (C) component, and optionally optional components such as a solvent, for example, using a three roll, planetary mixer, or likai machine.
  • a paste-like conductive composition can be produced.
  • the order which mixes said each component is arbitrary, may be mixed simultaneously and may be mixed sequentially.
  • a cured film can be formed by heating and thermosetting.
  • Application method is not particularly limited, and examples thereof include dispensing, jet dispensing, stencil printing, screen printing, pin transfer, and stamping.
  • the heating temperature can be, for example, 120 to 200 ° C., more preferably 150 to 175 ° C., and the heating time can be, for example, 1 to 120 hours, preferably 30 to 60 hours. is there.
  • a conductive circuit can be formed by applying the conductive composition of the present invention on a substrate (for example, a ceramic substrate such as LTCC or a glass / epoxy substrate) and then thermally curing it.
  • the conductive composition of the present invention can also be used as a die bonding agent.
  • a die bonding agent made of the conductive composition of the present invention to a predetermined part of a lead frame or a substrate (for example, Bare Cu lead frame, Ag plated Cu lead frame, PPF, Ag plated 42 alloy frame).
  • the semiconductor element can be mounted and thermally cured to bond the lead frame or the substrate and the semiconductor element.
  • the cured film thus obtained exhibits sufficient conductivity (for example, a specific resistance value of 1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm or less). Moreover, the adhesiveness (adhesion strength, adhesion resistance value) between the substrates is also good.
  • each conductive composition of the examples and comparative examples is made on an alumina substrate (120 mm ⁇ 20 mm, thickness 1.6 mm) using a stainless mask (200 mesh, resist 20 ⁇ m) so as to have a pattern as shown in FIG.
  • the object was screen printed. Next, it heated for 30 minutes with the ventilation drying machine hold
  • the resistance value X ( ⁇ ) at both ends of the cured film of the sample was measured using a 4261ALCR meter (manufactured by YHP).
  • the thickness Z ( ⁇ m) of the cured film 2 of the conductive composition on the alumina substrate 1 was measured using a surface roughness profile measuring machine Surfcom 590A (surface roughness profile measuring machine manufactured by Tokyo Seimitsu Co., Ltd.) (FIG. 1 ⁇ 2).
  • An AgPd electrode 3216 type capacitor component (capacitor electrode 6) is mounted so as to be in contact with the conductive composition 5 (FIG. 2-3), and a load of 1.0 ⁇ 0.5 N is applied evenly to the component.
  • a sample was obtained.
  • the conductive composition was cured under predetermined curing conditions (heated to 150 ° C. in 30 minutes and held at 150 ° C. for 30 minutes).
  • the resistance value between the upper part of the capacitor electrode 6 of the sample and the conductor (substrate electrode) within 1 mm from the coated part of the conductive composition 5 was measured by a four-terminal method (see FIG. 2-4).
  • the measured current value of the current source was 10 ⁇ 0.5 mA.
  • the average value was calculated from the measured values of 8 samples and used as the value of contact resistance.
  • Each conductive composition was screen-printed on a Bare Cu lead frame using a screen mask capable of forming 10 patterns of 1.5 mm ⁇ ⁇ 40 ⁇ mt.
  • Ten 2 mm square silicon chips were mounted so that the silicon surface was in contact with the conductive composition.
  • curing was performed under predetermined curing conditions (heating to 150 ° C. in 30 minutes and holding at 150 ° C. for 30 minutes).
  • the obtained sample was struck from the side surface using a strength tester MODEL-1605HTP (manufactured by Aiko Engineering Co., Ltd.), and the numerical value when the silicon chip was peeled was read.
  • the measurement was performed at a normal speed (25 ⁇ 5 ° C.) at a test speed of 12 ⁇ 1 mm / min when protruding from the side.
  • Viscosity change rate (%) (V2 ⁇ V1) / V1 ⁇ 100
  • D50 is 2 cups of silver-coated particles in a microspatella, taken in a 300 ml beaker, put 50 ml of a 0.5% sodium sulfosuccinate dioctyl ester solution, dispersed for 10 minutes with an ultrasonic homogenizer, and a light scattering analysis type particle size distribution analyzer. (A Coulter LS230 (manufactured by Beckman Coulter)) The average value of 50% cumulative diameter is D50.
  • Weight of silver coating layer It is a value calculated from the weight of the silver-coated particles and the core material measured by dissolving the silver-coated layer in nitric acid and removing silver.
  • Thickness of silver coating layer This is a value obtained by preparing a sample similar to the average thickness T and measuring it with a field emission scanning electron microscope (JEOL JSM-7500F) at a magnification of 10,000 to 30,000 times.
  • Resin 1 Bisphenol F type epoxy resin Bisphenol F type epoxy resin (epoxy equivalent: 160 to 175)
  • Resin 2 Aminophenol type epoxy resin N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropyloxy) aniline resin 3: PO modified epoxy resin Polyoxypropylene bisphenol A diglycidyl ether ( Epoxy equivalent 250-270)
  • Filler 1 Fumed silica Polydimethylsiloxane-treated fumed silica Volume-based average particle size: 0.25 ⁇ m
  • FIG. 3-1 is a SEM photograph of the silver-coated particles 1 at a magnification of 5000 times
  • FIG. 3-2 is a graph illustrating the measurement of the average thickness.
  • the silver-coated particles 1 were mixed with a water-soluble epoxy resin and cured. It is a SEM photograph of the section of hardened material.
  • Examples 1 to 6 using the flaky silver-coated particles of the present invention all had small specific resistance values and contact resistance values, and were excellent in adhesive strength.
  • Examples 3 to 6 using silver particles treated with oleic acid had little change in viscosity and were excellent in the stability of the conductive composition.
  • Comparative Example 1 using silver-coated particles having a small aspect ratio was inferior in specific resistance value and contact resistance value.
  • Examples 7 to 9 in Table 2 even if the thermosetting resin system is changed, the flaky silver-coated particles of the present invention are effective, and even if the amount of silver-coated particles is changed, the flakes of the present invention are effective. It can be seen that the silver-coated particles are effective.
  • the silver-coated particles of the (A) component are based on 100 parts by mass in total of the conductive composition ((A) component, (B) component and (C) component).
  • the adhesive strength was slightly inferior.
  • the specific resistance value and the contact resistance value are small even when the silver coating layer of the component (A) is 50 to 60% by mass of the total weight of the silver-coated particles.
  • the adhesive strength was also excellent.
  • Example 15 when spherical silver-coated particles having an aspect ratio T / D50 of 1.0 were used, a tendency to be slightly inferior in terms of contact resistance was observed.
  • a conductive composition that satisfies both cost reduction and good adhesion and expression of conductivity.
  • the conductive composition of the present invention is useful as a conductive circuit formation and die bonding agent.

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  • Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Conductive Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Die Bonding (AREA)

Abstract

L'invention porte sur une composition conductrice de l'électricité qui est relativement bon marché et qui présente des propriétés adhésives et une conductivité électrique satisfaisantes. La composition conductrice de l'électricité comprend : (A) des particules en forme de paillettes recouvertes d'argent qui sont choisies dans le groupe constitué par les particules de céramique recouvertes d'argent, les particules de verre recouvertes d'argent et les particules d'aluminium recouvertes d'argent, qui présentent un diamètre de particule moyen en volume (D50), mesuré par une technique de diffusion de lumière laser, de 1 à 10 µm, qui présentent une épaisseur moyenne (T), mesurée à l'aide d'un microscope électronique à balayage, de 0,3 à 10 µm et qui présentent un rapport de forme (T/D50) de 0,3 à 1,0 ; (B) une résine thermodurcissable et (C) un agent durcisseur. L'invention porte également sur un agent de fixage de puce comportant la composition conductrice de l'électricité.
PCT/JP2012/054882 2011-03-01 2012-02-28 Composition conductrice de l'électricité WO2012118061A1 (fr)

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CN201280010616.6A CN103391973B (zh) 2011-03-01 2012-02-28 导电性组合物
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JP2013206777A (ja) * 2012-03-29 2013-10-07 Dowa Electronics Materials Co Ltd 銀被覆フレーク状硝子粉およびその製造方法
JP2014177539A (ja) * 2013-03-14 2014-09-25 Cosmo Oil Lubricants Co Ltd 高熱伝導性エポキシ樹脂系組成物
JP2017082195A (ja) * 2015-10-29 2017-05-18 三菱マテリアル株式会社 樹脂組成物、接合体及び半導体装置
EP3216837A4 (fr) * 2015-04-16 2018-05-09 Furukawa Electric Co. Ltd. Film adhésif électroconducteur et film de découpage/fixation de puces
WO2018087858A1 (fr) * 2016-11-10 2018-05-17 京セラ株式会社 Composition de résine liante pour semi-conducteur, feuille liante pour semi-conducteur et dispositif semi-conducteur l'utilisant
WO2019027023A1 (fr) * 2017-08-03 2019-02-07 パウダーテック株式会社 Particules composites, poudre, composition de résine et corps moulé
TWI682405B (zh) * 2015-01-14 2020-01-11 日商東洋紡股份有限公司 導電性銀糊劑
CN113257456A (zh) * 2021-05-12 2021-08-13 浙江奕成科技有限公司 一种异质结太阳能电池用低成本导电浆料及其制备方法
JP2021168325A (ja) * 2020-04-09 2021-10-21 株式会社東芝 超電導コイルの製造方法、および、電気機器の製造方法

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KR101618093B1 (ko) * 2014-03-17 2016-05-09 주식회사 상보 도전막 형성을 위한 유연 기판용 전도성 페이스트 조성물 및 이의 제조방법
US10266729B2 (en) * 2015-03-02 2019-04-23 Three Bond Co., Ltd. Thermocurable electroconductive adhesive
JP2017008160A (ja) * 2015-06-18 2017-01-12 京セラ株式会社 ダイボンディングペーストの製造方法およびダイボンディングペースト
KR102526024B1 (ko) * 2015-11-26 2023-04-25 가부시끼가이샤 쓰리본드 열경화성 조성물 및 그를 이용한 도전성 접착제
CN107633894A (zh) * 2016-07-19 2018-01-26 翌骅实业股份有限公司 具改质金属粒子的导电胶及其制造方法及太阳能电池组件
CN107424964A (zh) * 2017-07-27 2017-12-01 武汉市三选科技有限公司 底部填充组成物及使用其之底部填充方法与电子组装组件
JP2020139020A (ja) * 2019-02-27 2020-09-03 ナミックス株式会社 導電性接着剤
CN109979686A (zh) * 2019-04-19 2019-07-05 东莞市银屏电子科技有限公司 一种低温导电铜浆及其制备方法
CN111462935A (zh) * 2020-05-12 2020-07-28 无锡市伍豪机械设备有限公司 导电性颗粒及其制造方法

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JP2006147351A (ja) * 2004-11-19 2006-06-08 Mitsui Mining & Smelting Co Ltd 導電性複合粉末及びその製造方法
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013206777A (ja) * 2012-03-29 2013-10-07 Dowa Electronics Materials Co Ltd 銀被覆フレーク状硝子粉およびその製造方法
JP2014177539A (ja) * 2013-03-14 2014-09-25 Cosmo Oil Lubricants Co Ltd 高熱伝導性エポキシ樹脂系組成物
TWI682405B (zh) * 2015-01-14 2020-01-11 日商東洋紡股份有限公司 導電性銀糊劑
EP3216837A4 (fr) * 2015-04-16 2018-05-09 Furukawa Electric Co. Ltd. Film adhésif électroconducteur et film de découpage/fixation de puces
JP2017082195A (ja) * 2015-10-29 2017-05-18 三菱マテリアル株式会社 樹脂組成物、接合体及び半導体装置
WO2018087858A1 (fr) * 2016-11-10 2018-05-17 京セラ株式会社 Composition de résine liante pour semi-conducteur, feuille liante pour semi-conducteur et dispositif semi-conducteur l'utilisant
US10767085B2 (en) 2016-11-10 2020-09-08 Kyocera Corporation Semiconductor-bonding resin composition, semiconductor-bonding sheet, and semiconductor device using semiconductor-bonding sheet
WO2019027023A1 (fr) * 2017-08-03 2019-02-07 パウダーテック株式会社 Particules composites, poudre, composition de résine et corps moulé
JP2021168325A (ja) * 2020-04-09 2021-10-21 株式会社東芝 超電導コイルの製造方法、および、電気機器の製造方法
JP7395413B2 (ja) 2020-04-09 2023-12-11 株式会社東芝 超電導コイルの製造方法、および、電気機器の製造方法
CN113257456A (zh) * 2021-05-12 2021-08-13 浙江奕成科技有限公司 一种异质结太阳能电池用低成本导电浆料及其制备方法

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CN103391973A (zh) 2013-11-13
JPWO2012118061A1 (ja) 2014-07-07
TW201241146A (en) 2012-10-16
KR20140017583A (ko) 2014-02-11
JP5927177B2 (ja) 2016-06-01
CN103391973B (zh) 2017-02-08
KR101971746B1 (ko) 2019-04-23
TWI550053B (zh) 2016-09-21

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