WO2009122467A1 - Method for joining metallic members, metallic member joined product, and method for manufacturing bump for electric circuit connection - Google Patents

Method for joining metallic members, metallic member joined product, and method for manufacturing bump for electric circuit connection Download PDF

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Publication number
WO2009122467A1
WO2009122467A1 PCT/JP2008/002045 JP2008002045W WO2009122467A1 WO 2009122467 A1 WO2009122467 A1 WO 2009122467A1 JP 2008002045 W JP2008002045 W JP 2008002045W WO 2009122467 A1 WO2009122467 A1 WO 2009122467A1
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WIPO (PCT)
Prior art keywords
metal
copper
silver
gas
hydrogen gas
Prior art date
Application number
PCT/JP2008/002045
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French (fr)
Japanese (ja)
Inventor
増田涼子
工藤康全
一色実
浅見英知
山川君男
峯勝利
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ニホンハンダ株式会社
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Priority to JP2010505047A priority Critical patent/JPWO2009122467A1/en
Publication of WO2009122467A1 publication Critical patent/WO2009122467A1/en

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
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    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
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Definitions

  • the present invention relates to a method for joining metal members using a paste-like metal particle composition comprising heat-sinterable metal particles and a volatile dispersion medium, a metal member assembly obtained by using the joining method, and
  • the present invention also relates to a method for manufacturing a bump for connecting an electric circuit.
  • a conductive / thermal conductive paste obtained by dispersing a metal powder such as silver, copper, or nickel in a liquid thermosetting resin composition is cured by heating to form a conductive / thermal conductive film. Therefore, formation of conductive circuits on printed circuit boards, formation of various electronic components such as resistors and capacitors, and electrodes of various display elements, formation of conductive films for electromagnetic wave shielding, capacitors, resistors, diodes, memories, arithmetic elements (CPU) and other chip components to substrates, formation of solar cell electrodes, especially formation of solar cell electrodes that cannot be processed at high temperatures due to the use of amorphous silicon semiconductors, multilayer ceramic capacitors, multilayer ceramic inductors It is used for forming external electrodes of chip-type ceramic electronic components such as multilayer ceramic actuators.
  • the present inventors when heated, the paste-like silver composition composed of silver powder and a volatile dispersion medium volatilizes the volatile dispersion medium and sinters the silver powder, An international application was made to find out that it was solid silver having extremely high electrical conductivity and thermal conductivity, and useful for joining metal members and forming conductive circuits (WO2006 / 126614, WO2007 / 034833).
  • JP 2007-083288 a copper paste or silver paste coated with an organic amine is applied to a metal layer (eg, a copper clad laminate) and a metal layer (eg, an electrode of an electronic device), and the coated surface is A method is disclosed in which both metal layers are brought into close contact with each other after the plasma treatment, and the metal layers are bonded together by heating and firing in a reducing atmosphere, but this is a complicated method.
  • organic amines may volatilize during heating and firing, which may cause odor and safety and health problems.
  • An object of the present invention is to provide a method of strongly joining metal members without corrosion or discoloration without plasma treatment in joining of metal members by sintering a paste-like metal particle composition. Further, it is to provide a metal member joined body in which the metal member is firmly joined without being corroded or discolored, and further, firmly joined to the electric circuit connecting pad portion or the electric circuit connecting electrode portion. Another object of the present invention is to provide a bump for connecting an electric circuit.
  • This purpose is “[1] (A) Paste form comprising heat-sinterable metal particles having an average particle size of more than 0.1 ⁇ m and not more than 50 ⁇ m and coated with a non-amine water-repellent organic substance, and (B) a volatile dispersion medium A metal particle composition is interposed between a plurality of metal members, and the volatile dispersion medium is volatilized by heating at 70 ° C. or more and 400 ° C. or less in a reducing gas to sinter the metal particles.
  • a method for joining metal members comprising joining metal members together.
  • the reducing gas is hydrogen gas or a hydrogen gas-containing gas.
  • the metal of the heat-sinterable metal particles is silver, silver alloy, copper or copper alloy, and the metal of the metal member is copper, silver, gold, platinum, palladium, or an alloy of each of these metals
  • the non-amine water-repellent organic substance is a high / intermediate fatty acid or a derivative thereof
  • the metal of the heat-sinterable metal particles is silver, a silver alloy, copper, or a copper alloy
  • the metal of the metal member is copper Silver, gold, platinum, palladium, or an alloy of these metals
  • the reducing gas is hydrogen gas or a hydrogen gas-containing gas
  • the non-amine water-repellent organic substance is a high / intermediate fatty acid or a derivative thereof
  • the metal of the heat-sinterable metal particles is silver, silver alloy, copper or
  • the joining method according to [1], which is a copper alloy, and the metal of the metal member is copper, silver, gold, platinum, palladium, or an alloy of these metals.
  • the hydrogen gas-containing gas is a mixture of hydrogen gas and inert gas, the concentration of hydrogen gas is 1 to 40% by volume, the high / intermediate fatty acid has 6 to 24 carbon atoms, and its derivatives are
  • the joining method according to [8] which is a high / intermediate fatty acid metal salt (excluding an alkali metal salt), a high / intermediate fatty acid amide, or a high / intermediate fatty acid ester. Is achieved.
  • This purpose is also “[10] Heat-sinterable metal particles having an average particle size of more than 0.1 ⁇ m and less than 50 ⁇ m and coated with a non-amine water-repellent organic substance are heated and fired in a reducing gas.
  • a metal member assembly characterized by being formed by bonding.
  • the reducing gas is hydrogen gas or a hydrogen gas-containing gas
  • the non-amine water-repellent organic substance is a high / intermediate fatty acid or a derivative thereof
  • the metal of the heat-sinterable metal particles is silver, silver alloy, copper or
  • the metal member assembly according to [10] which is a copper alloy
  • the metal of the metal member is copper, silver, gold, platinum, palladium, or an alloy of these metals.
  • the hydrogen gas-containing gas is a mixture of hydrogen gas and inert gas, the concentration of hydrogen gas is 1 to 40% by volume, the high / intermediate fatty acid has 6 to 24 carbon atoms, and its derivatives are
  • the metal member assembly according to [11] which is a high / intermediate fatty acid metal salt (excluding alkali metal salts), a high / intermediate fatty acid amide, or a high / intermediate fatty acid ester. Is achieved.
  • the metal member bonded body is coated with the non-amine water-repellent organic material using the above bonding method, that is, “(A) The average particle diameter is larger than 0.1 ⁇ m and not larger than 50 ⁇ m in [1].
  • the paste-like metal particle composition comprising the heated sinterable metal particles and (B) the volatile dispersion medium is interposed between the plurality of metal members, and heated at 70 ° C. to 400 ° C. in a reducing gas.
  • the metal member joining method is characterized in that the volatile dispersion medium is volatilized and the metal particles are sintered to join together a plurality of metal members. ] To [12].
  • This purpose is also “[13] (A) Paste form comprising heat-sinterable metal particles having an average particle size of more than 0.1 ⁇ m and not more than 50 ⁇ m and coated with a non-amine water-repellent organic substance, and (B) a volatile dispersion medium
  • the metal particle composition is applied in the form of dots on an electric circuit connecting pad on a semiconductor element or an electric circuit connecting electrode on a substrate, and the volatilization is effected by heating at 70 ° C. to 400 ° C. in a reducing gas.
  • a method for producing a bump for connecting an electric circuit comprising volatilizing a conductive dispersion medium and sintering the metal particles to form bumps made of metal particles on a semiconductor element or a substrate.
  • the reducing gas is hydrogen gas or a hydrogen gas-containing gas
  • the non-amine water-repellent organic substance is a high / intermediate fatty acid or derivative thereof
  • the metal of the heat-sinterable metal particles is silver, silver alloy, copper or It is a copper alloy
  • the metal of the electric circuit connecting pad part or the electric circuit connecting electrode part on the substrate is copper, silver, gold, platinum, palladium, or an alloy of these metals.
  • the hydrogen gas-containing gas is a mixture of hydrogen gas and inert gas, the concentration of hydrogen gas is 1 to 40% by volume, the high and intermediate fatty acids have 6 to 24 carbon atoms, and their derivatives are
  • the volatile dispersion medium in the composition is volatilized by heating the paste-like metal particle composition even when joining between metal members that are easily oxidized and corroded or discolored.
  • the heat-sinterable metal particles (A) are sintered and become solid, and the metal member can be firmly bonded without being corroded or discolored.
  • the average particle diameter is larger than 0.1 ⁇ m and not more than 50 ⁇ m between the plurality of metal members.
  • the metal members are firmly bonded without being corroded or discolored. According to the method for manufacturing an electric circuit connecting bump of the present invention, even if the electric circuit connecting pad part on the semiconductor element or the electric circuit connecting electrode part on the substrate is oxidized and easily made corroded or discolored, A bump made of metal particles firmly bonded to them is formed.
  • FIG. 2 is a sectional view taken along line XX in FIG.
  • a Test specimen for measuring bonding strength 1 Copper substrate 2 Paste-like silver particle composition or paste-like copper particle composition (solid silver or solid copper after heat sintering) 3 Silver chip or copper chip
  • the joining method of the present invention comprises (A) heat-sinterable metal particles having a mean particle size of more than 0.1 ⁇ m and not more than 50 ⁇ m and coated with a non-amine water-repellent organic substance, and (B) a volatile dispersion medium.
  • the paste-like metal particle composition is interposed between a plurality of metal members, and the volatile dispersion medium is volatilized by heating at 70 ° C. to 400 ° C. in a reducing gas to sinter the metal particles.
  • a plurality of metal members are joined together.
  • the average particle size of the heat-sinterable metal particles (A) is larger than 0.1 ⁇ m and not larger than 50 ⁇ m.
  • This average particle diameter is an average particle diameter of primary particles obtained by a laser diffraction / scattering particle size distribution measurement method.
  • the average particle diameter exceeds 50 ⁇ m, the sinterability of the heat-sinterable metal particles is lowered, so that the average particle diameter is preferably small. For this reason, it is preferable that it is 20 micrometers or less, and it is especially preferable that it is 10 micrometers or less.
  • the average particle size is 0.1 ⁇ m or less, the surface activity is too strong, the storage stability of the paste-like metal particle composition is lowered, and the bonding strength at the time of heat sintering becomes non-uniform.
  • the diameter is greater than 0.1 ⁇ m.
  • the average particle size is preferably 0.2 ⁇ m or more. That is, the average particle size range of the heat-sinterable metal particles (A) is preferably 0.2 to 10 ⁇ m.
  • the material of the heat-sinterable metal particles is solid at room temperature, and only needs to be easily sintered by heating.
  • Gold, silver, copper, palladium, nickel, tin, aluminum, and alloys of these metals are exemplified.
  • a metal compound is illustrated.
  • silver, copper, and nickel are preferable, silver, silver alloy, copper, and copper alloy are more preferable, and silver or copper is preferable in terms of heat-sinterability, thermal conductivity of the sintered product, and conductivity.
  • the silver particles may have a part of the surface or inside thereof that may be silver oxide or silver peroxide, and the entire surface may be silver oxide or silver peroxide.
  • the copper particles may have copper oxide on the surface or part of the inside, or the entire surface may be copper oxide.
  • the heat-sinterable metal particles are usually made of a single material, but may be a mixture of particles made of a plurality of materials.
  • Heat-sinterable metal particles are made of metal (for example, copper, nickel, or aluminum) particles whose surfaces are plated with the heat-sinterable metal (for example, silver), and the surface is made of the heat-sinterable metal (for example, silver).
  • Plated resin for example, epoxy resin, polyethersulfone resin
  • the shape of the heat-sinterable metal particles is not particularly limited, and examples thereof include a spherical shape, an elliptical spherical shape, a spindle shape, a granular shape, a substantially cubic shape, a flake shape, and an indefinite shape.
  • the shape is preferably spherical, granular or flaky from the viewpoint of storage stability.
  • Preferred heat-sinterable metal particles are silver particles made by the reduction method and copper particles made by the reduction method. Many methods for producing silver particles by the reduction method have been proposed.
  • an aqueous solution of a reducing agent such as formalin is added to an aqueous solution of silver nitrate by adding an aqueous solution of sodium hydroxide to an aqueous solution of silver nitrate. It is produced by reducing silver to form a silver particle dispersion, filtering the dispersion, washing the filtration residue with water, and drying.
  • the copper particles obtained by the reduction method are usually prepared by contact-reacting a copper sulfate aqueous solution and a hydrazine aqueous solution to reduce and precipitate copper powder, washing with pure water, and drying (see, for example, JP-A-59-59). 11630).
  • the surface of the heat-sinterable metal particles is coated or treated with a non-amine water-repellent organic substance.
  • the non-amine water-repellent organic material preferably has excellent lubricity, and includes high / intermediate fatty acids, high / intermediate fatty acid metal salts (excluding alkali metal salts), high / intermediate fatty acid amides and high / intermediate fatty acid esters. Illustrated. High and intermediate fatty acids are particularly preferred in terms of coating effect and treatment effect.
  • the higher fatty acid is a fatty acid having 15 or more carbon atoms, and includes pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), 12-hydroxyoctadecanoic acid (12-hydroxystearic acid), eicosanoic acid ( Linear saturated fatty acids such as arachidic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (serotic acid), octacosanoic acid (montanic acid); 2-pentylnonanoic acid, 2-hexyldecanoic acid, 2- Examples include branched saturated fatty acids such as heptyldodecanoic acid and isostearic acid; unsaturated fatty acids such as palmitoleic acid, oleic acid, iso
  • Intermediate fatty acids are fatty acids having 6 to 14 carbon atoms, such as hexanoic acid (caproic acid), heptanoic acid, octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, Linear saturated fatty acids such as dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid); isohexanoic acid, isoheptanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, 2-propylheptanoic acid, isodecanoic acid, Illustrative examples include branched saturated fatty acids such as isoundecanoic acid, 2-butyloctanoic acid, isododecanoic acid and isotridecanoic acid; and unsaturated fatty acids such as 10-unde
  • the coating amount of the non-amine water-repellent organic substance varies depending on the particle size, specific surface area, shape, etc. of the metal particles, but is preferably 0.01 to 3% by weight of the heat-sinterable metal particles (A), preferably 0.1 to 2% by weight is more preferred. If the amount is too small, the heat-sinterable metal particles (A) tend to agglomerate and the storage stability is lowered.As a result, the bonding strength at the time of heat-sintering becomes uneven, and if too large, the heat-sinterable metal particles (A) This is because the heat sinterability of) decreases.
  • the adhesion amount of the non-amine water-repellent organic substance can be measured by a usual method. For example, a method of measuring weight loss by heating above the boiling point of a non-amine water-repellent organic substance in nitrogen gas, heating sinterable metal particles (A) in an oxygen stream and heating sinterable metal particles (A) (A) in an oxygen stream and heating sinterable metal particles (A) (A) is changed to carbon dioxide and quantitative analysis is performed by infrared absorption spectroscopy.
  • flaky heat-sinterable metal particles with non-amine water-repellent organic substances adhered to them are placed in a ball mill with spherical metal particles and non-amine water-repellent organic substances, and the metal particles are beaten with balls.
  • a ball mill with spherical metal particles and non-amine water-repellent organic substances, and the metal particles are beaten with balls.
  • Amine-based water-repellent organic materials are put together with ceramic balls into a rotary drum device (for example, a ball mill), and metal particles are beaten with the balls, so that flake-like heat-sintered with non-amine-based water-repellent organic materials attached.
  • Metal particles can be produced.
  • non-amine water-repellent organic substances such as high / intermediate fatty acids, high / intermediate fatty acid metal salts (except alkali metal salts), high / intermediate fatty acid esters, and high / intermediate fatty acid amides for improving lubricity And adheres to the surface of the flaky heat-sinterable metal particles.
  • the surface of the heat-sinterable metal particles (A) may be covered with more than half of such high / intermediate fatty acid, but it is preferable that the surface is covered entirely.
  • the heat-sinterable metal particles (A) whose metal surface is coated with a non-amine water-repellent organic substance exhibit water repellency.
  • the heat-sinterable metal particles (A) whose surfaces are coated with a non-amine water-repellent organic substance are immersed in the solution of the non-amine-type water-repellent organic substance, and then the metal particles are taken out and dried. It can also be manufactured.
  • the volatile dispersion medium (B) is blended in order to make powdery metal particles into a paste.
  • the paste form includes a cream form and a slurry form.
  • the heat-sinterable metal particles (A) are silver particles or copper particles
  • the dispersion medium is volatilized during sintering, the silver particles and copper particles are easily sintered and can be easily used as a bonding agent. Because.
  • the boiling point of the volatile dispersion medium is preferably 60 ° C to 300 ° C. When the boiling point is less than 60 ° C., the solvent easily evaporates during the preparation of the paste-like metal particle composition, and when the boiling point is higher than 300 ° C., the volatile dispersion medium (B) remains even after heating. Because it might be.
  • Such a volatile dispersion medium (B) is composed of a volatile hydrocarbon compound composed of carbon atoms and hydrogen atoms, a volatile organic compound composed of carbon atoms, hydrogen atoms and oxygen atoms, carbon atoms, hydrogen atoms and nitrogen atoms. It is selected from volatile organic compounds, volatile organic compounds composed of carbon atoms, hydrogen atoms, oxygen atoms and nitrogen atoms, a mixture of hydrophilic volatile organic compounds of the volatile organic compounds and water, and the like. These are all liquid at room temperature.
  • the water is preferably pure water, and its electric conductivity is preferably 100 ⁇ S / cm or less, more preferably 10 ⁇ S / cm or less.
  • the pure water production method may be a normal method, and examples include an ion exchange method, a reverse osmosis method, and a distillation method.
  • volatile organic compounds composed of carbon atoms, hydrogen atoms and oxygen atoms
  • Monohydric alcohol ethylene glycol monomethyl ether (methyl cellosolve, methyl carbitol), ethylene glycol monoethyl ether (emethyl cellosolve, ethyl carbitol), ethylene glycol monopropyl ether (propyl cellosolve, propyl carbitol), ethylene glycol mono Ethers such as butyl ether (butyl cellosolve, butyl carbitol), propylene glycol monomethyl ether, methylmethoxybutanol Volatile monohydric alcohols having binding; benzyl alcohol, volatile aralkyl alcohols such as 2-phenylethyl alcohol, ethylene glycol, propylene glycol, volatile polyhydric aliphatic alcohols such as glycerin are exemplified.
  • volatile organic compounds composed of carbon atoms, hydrogen atoms and nitrogen atoms include volatile alkyl nitriles such as acetonitrile and propionitrile.
  • volatile organic compounds composed of carbon atoms, hydrogen atoms, oxygen atoms and nitrogen atoms include volatile carboxylic acid amides such as acetamide and N, N-dimethylformamide.
  • Other examples include low molecular weight volatile silicone oils and volatile organic modified silicone oils.
  • the blending amount of the volatile dispersion medium (B) is an amount sufficient to make the heat-sinterable metal particles (A) into a paste at room temperature.
  • the amount sufficient to make a paste varies, but the specific For example, the amount is 3 to 30 parts by weight per 100 parts by weight of the heat-sinterable metal particles (A).
  • non-metallic powder other than the heat-sinterable metal particles (A), metal compound, metal complex, thixotropic agent, Additives such as stabilizers and colorants may be added in small amounts or in trace amounts.
  • the paste-like metal particle composition used in the present invention comprises (A) a heat-sinterable metal particle having an average particle size of greater than 0.1 ⁇ m and 50 ⁇ m or less and coated with a non-amine water-repellent organic substance, and (B)
  • the volatile dispersion medium can be easily manufactured by putting it into a mixer and stirring and mixing it until it becomes a uniform paste.
  • the paste-like metal particle composition used in the present invention is a mixture of heat-sinterable metal particles (A) and a volatile dispersion medium (B), and is paste-like at room temperature.
  • the paste form includes a cream form and a slurry form. By making it into a paste, it can be discharged in a thin line from a cylinder or nozzle, and printing with a metal mask is easy.
  • the thickness of the paste-like metal particle composition interposed between a plurality of metal members is not particularly limited as long as the necessary bonding strength is exhibited by heat sintering of the heat sinterable metal particles (A). . Usually, it is 5 ⁇ m or more and 1200 ⁇ m or less.
  • the applied paste-like metal particle composition volatilizes the volatile dispersion medium in the composition by heating, and the heat-sinterable metal particles (A) sinter. It is a to-be-joined body to join.
  • the material of the metal member include gold, silver, copper, platinum, palladium, nickel, tin, aluminum, and alloys of these metals. Among these, copper, silver, gold, platinum, palladium, or an alloy of these metals is preferable in terms of conductivity and bondability.
  • the metal member may be plated with the metal. Examples of the metal member include a lead frame, a printed circuit board, a semiconductor chip, and a heat sink, all or part of which is made of metal.
  • the paste-like metal particle composition is interposed between a plurality of metal members, and the volatile dispersion medium is volatilized by heating at 70 ° C. or more and 400 ° C. or less in a reducing gas.
  • the metal particles are sintered to join a plurality of metal members.
  • the paste-like metal particle composition is interposed between metal members and heated in a gas containing oxygen gas, there are problems such as corrosion and discoloration due to oxidation of the metal members.
  • an inert gas there is a problem that the metal particles in the paste-like metal particle composition are not sufficiently sintered and the bonding strength is lowered.
  • the heat-sinterable metal particles for heat-sinterable metal particles (A) in the paste-like metal particle composition used for joining and the surface metal of the metal member are preferably the same metal or metal alloy. Then, it is preferable that the metals are easy to form an alloy.
  • the reducing gas examples include hydrogen gas, carbon monoxide, and ammonia decomposition gas, but hydrogen gas is preferable.
  • the reducing gas need not be a pure product, and may be a mixture with an inert gas.
  • Specific examples of the inert gas include helium gas, argon gas, and nitrogen gas, and nitrogen gas is particularly preferable.
  • the ratio of the reducing gas component to the inert gas component in the reducing gas is not limited, but when the reducing gas component is hydrogen gas, it is more preferably 1 to 40% by volume.
  • the ratio of hydrogen gas is less than 1% by volume, the effect of reducing and removing the surface oxides of easily oxidized metal members such as copper and copper alloys is poor, and heating in the paste-like metal particle composition
  • the sinterability of the sinterable metal particles (A) is not sufficient and the bonding strength is reduced. This is because if the ratio of hydrogen gas exceeds 40% by volume, the danger of handling as a combustible gas increases.
  • the reducing gas is a reducing gas called a forming gas composed of 5 to 15% by volume of hydrogen gas and 95 to 85% by volume of nitrogen gas.
  • the reducing gas does not contain oxygen gas, even if it is contained, the reducing gas is preferably as small as possible in order to prevent oxidation and danger of the metal member, and particularly preferably 100 ppm or less.
  • the metal member does not corrode or discolor due to oxidation, and the paste-like metal particle composition is heated and fired in the paste-like metal particle composition.
  • the cohesive metal particles (A) can be sufficiently sintered to firmly join the metal members.
  • the volatile dispersion medium is volatilized.
  • the paste-like metal particle composition of the present invention is heated to a temperature equal to or higher than the sintering temperature of the heat-sinterable metal particles (A), whereby the volatile dispersion medium (B) is volatilized, and the metal particles ( A) sinters and becomes a solid metal having excellent conductivity and thermal conductivity, and joins metal members together. Pressure or ultrasonic vibration may be applied during the heating of the paste-like metal particle composition.
  • the volatile dispersion medium (B) is volatilized, and then the heat-sinterable metal particles (A) may be sintered together, and with the volatilization of the volatile dispersion medium (B), the heat-sinterable metal particles ( A) may be sintered together.
  • the heat-sinterable metal particles (A) are silver particles, since silver has inherently high strength and extremely high electrical and thermal conductivity, the sintered product of silver particles also has high strength and extremely high. It has electrical conductivity and thermal conductivity.
  • the heat-sinterable metal particles (A) are copper particles, copper originally has extremely high electrical and thermal conductivity, so the sintered product of copper particles also has extremely high electrical and thermal conductivity.
  • the heating temperature at this time may be a temperature at which the volatile dispersion medium (B) is volatilized and the heat-sinterable metal particles (A) can be sintered, and is usually 70 ° C. or higher, and more preferably 150 ° C. or higher. .
  • the temperature must be 400 ° C. or less, more preferably 300 ° C. It is as follows.
  • the volatile dispersion medium (B) is volatilized by heating, and the heat-sinterable metal particles (A) are sintered together.
  • the metal members that were in contact such as a gold-plated substrate, silver substrate, silver-plated metal substrate, copper substrate, aluminum substrate, nickel-plated substrate, tin-plated metal substrate, etc. Since it adheres firmly to a substrate and firmly adheres to a metal part such as an electrode on an electrically insulating substrate, the bonding method of the present invention is an electronic component, an electronic device, an electrical component, and an electrical device having a metal substrate and a metal part. It is useful for joining such as.
  • Such bonding includes bonding of chip parts such as capacitors and resistors and circuit boards, bonding of semiconductor chips such as diodes, memories, ICs, and CPUs to lead frames or circuit boards, and high-heat generation CPU chips and cooling plates.
  • chip parts such as capacitors and resistors and circuit boards
  • semiconductor chips such as diodes, memories, ICs, and CPUs to lead frames or circuit boards
  • high-heat generation CPU chips and cooling plates are exemplified.
  • the heat-sinterable metal particles coated with a non-amine water-repellent organic substance having an average particle size of more than 0.1 ⁇ m and 50 ⁇ m or less are reduced between a plurality of metal members. It is characterized by being heated and sintered in a reactive gas. Metal member, heat sinterable metal particles having an average particle size greater than 0.1 ⁇ m and less than 50 ⁇ m and coated with a non-amine water-repellent organic substance, reducing gas, and heat sintering Is as described above.
  • the thickness of the heat-sintered metal layer interposed between the plurality of metal members is not particularly limited as long as the necessary bond strength is exhibited. Usually, it is 3 ⁇ m or more and 1000 ⁇ m or less.
  • the metal member assembly of the present invention is a metal member which is easily oxidized and corroded or discolored, the average particle size is between 0.1 ⁇ m and 50 ⁇ m or less between the plurality of metal members. Since the heat-sinterable metal particles coated with the water-repellent organic material are heat-sintered in a reducing gas, the metal member is firmly bonded without being corroded or discolored.
  • a metal member joined body As such a metal member joined body, a joined body of a chip component such as a capacitor or a resistor and a circuit board, a joined body of a semiconductor chip such as a diode, memory, IC, or CPU and a lead frame or a circuit board, a high heat generating body A joined body of a CPU chip and a cooling plate is exemplified.
  • the volatile dispersion medium (B) is volatilized by heating, and the heat-sinterable metal particles (A) are sintered together.
  • the volatile dispersion medium is volatilized and the metal particles are sintered together, Metal bumps can be manufactured on a semiconductor element or substrate.
  • the silver chip or the copper substrate on which the copper chip is mounted is placed in a gas flow furnace at room temperature, air is replaced with a predetermined gas, and a temperature rising rate from room temperature is 1 ° C./minute while flowing a predetermined gas at a flow rate of 1 liter / min.
  • the temperature was raised to 300 ° C. in seconds, held at 300 ° C. for 1 hour, then cooled to room temperature and joined.
  • the test specimen for bonding strength measurement thus obtained was set on a test specimen fixture of an adhesive strength tester, and the side surface of the silver chip or copper chip was pressed with a pressing bar of the adhesive strength tester at a thickness rate of 23 mm / min.
  • the adhesive strength (unit: N (kgf)) was determined by the load when the joint was sheared and pressed.
  • the average value of the four bond strengths was defined as the bond strength.
  • Example 1 Commercially available silver particles produced by a reduction method and coated on the surface with stearic acid (shape: granular, average particle size of primary particles: 1.1 ⁇ m, amount of stearic acid as non-amine water-repellent organic substance: 0.3
  • 2- (2butoxyethoxy) ethane acetate manufactured by Wako Pure Chemical Industries, Ltd., reagent grade 1
  • reagent grade 1 2- (2butoxyethoxy) ethane acetate
  • a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume is used to produce a specimen for hardness measurement and a specimen for bonding strength measurement in a gas flow furnace.
  • These test specimens were measured and evaluated for hardness, bonding strength, and oxidation of the copper substrate, and the results are summarized in Table 1. From the above results, it was found that this joining method is useful for strongly sintering the silver particles in the paste-like silver particle composition and strongly joining the copper substrate and the silver chip without being oxidized.
  • Example 2 Into a ball mill, silver particles (shape: granular, average primary particle size: 1.0 ⁇ m, uncoated with non-amine water-repellent organic substance) produced by a commercially available reduction method are added, and oleic acid is added. By operation, flaky silver particles whose surfaces are coated with oleic acid (average particle size of primary particles: 3.0 ⁇ m, oleic acid amount of non-amine water-repellent organic substance: 0.3% by weight) are prepared. did.
  • a pasty silver particle composition was prepared under the same conditions as in Example 1 except that the flaky silver particles were used in place of the silver particles used in Example 1.
  • a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume is used to produce a specimen for hardness measurement and a specimen for bonding strength measurement in a gas flow furnace. did.
  • These test specimens were measured and evaluated for hardness, bonding strength, and oxidation of the copper substrate, and the results are summarized in Table 1. From the above results, it was found that this joining method is useful for strongly sintering the silver particles in the paste-like silver particle composition and strongly joining the copper substrate and the silver chip without being oxidized.
  • Example 3 In Example 1, as the reducing gas, instead of the mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume, the hydrogen gas concentration is 5% by volume and the nitrogen gas concentration is 95% by volume.
  • a test specimen for hardness measurement and a test specimen for joint strength measurement were prepared under the same conditions as in Example 1 except that a mixed gas was used. Hardness, joint strength, and oxidation of the copper substrate Were measured and evaluated, and the results are summarized in Table 1. From the above results, it was found that this joining method is useful for strongly sintering the silver particles in the paste-like silver particle composition and strongly joining the copper substrate and the silver chip without being oxidized.
  • Example 4 In Example 1, as a reducing gas, instead of a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume, the hydrogen gas concentration is 20% by volume and the nitrogen gas concentration is 80% by volume.
  • a test specimen for hardness measurement and a test specimen for bonding strength measurement were prepared under the same conditions as in Example 1 except that a mixed gas was used, and the hardness, bonding strength, and oxidation of the copper substrate were measured. Measurement and evaluation were performed, and the results are summarized in Table 1. From the above results, it was found that this joining method is useful for strongly sintering the silver particles in the paste-like silver particle composition and strongly joining the copper substrate and the silver chip without being oxidized.
  • Example 5 instead of the stearic acid-coated silver particles used in Example 1, silver particles produced by the reduction method and coated on the surface with lauric acid (shape: granular, average particle diameter of primary particles: 1.1 ⁇ m, non-amine system) A paste-like silver particle composition was prepared under the same conditions as in Example 1 except that the water-repellent organic substance lauric acid amount: 0.2 wt% was used.
  • a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume is used to produce a specimen for hardness measurement and a specimen for bonding strength measurement in a gas flow furnace.
  • These test specimens were measured and evaluated for hardness, bonding strength, and oxidation of the copper substrate, and the results are summarized in Table 1. From the above results, it was found that this joining method is useful for strongly sintering the silver particles in the paste-like silver particle composition and strongly joining the copper substrate and the silver chip without being oxidized.
  • Example 6 Commercially available copper particles manufactured by the reduction method and coated with stearic acid on the surface (shape: granular, average particle size of primary particles: 1.1 ⁇ m, amount of stearic acid as non-amine water-repellent organic substance: 0.3
  • shape granular, average particle size of primary particles: 1.1 ⁇ m
  • amount of stearic acid as non-amine water-repellent organic substance 0.3
  • 2- (2butoxyethoxy) ethane acetate manufactured by Wako Pure Chemical Industries, Ltd., reagent grade 1
  • a paste-like copper particle composition was prepared.
  • a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume is used to produce a specimen for hardness measurement and a specimen for bonding strength measurement in a gas flow furnace.
  • These test specimens were measured and evaluated for hardness, bonding strength, and oxidation of the copper substrate and the copper chip, and the results are shown in Table 1. From the above results, it has been found that this joining method is useful for strongly sintering the copper particles in the paste-like copper particle composition and strongly joining the copper substrate and the copper chip without being oxidized.
  • Example 7 Copper particles (shape: granular, average particle size of primary particles: 1.0 ⁇ m, uncoated with non-amine water-repellent organic substance) produced by a commercially available reduction method are put into a ball mill, and oleic acid is added. By operating, flaky copper particles whose surface is coated with oleic acid (average particle size of primary particles: 3.0 ⁇ m, oleic acid amount of non-amine water-repellent organic substance: 0.3% by weight) are prepared. did.
  • a paste-like copper particle composition was prepared under the same conditions as in Example 6 except that the flaky copper particles were used instead of the copper particles used in Example 6.
  • a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume is used to produce a specimen for hardness measurement and a specimen for bonding strength measurement in a gas flow furnace. did.
  • These test specimens were measured and evaluated for hardness, bonding strength, and oxidation of the copper substrate and the copper chip, and the results are shown in Table 1. From the above results, it has been found that this joining method is useful for strongly sintering the copper particles in the paste-like copper particle composition and strongly joining the copper substrate and the copper chip without being oxidized.
  • Example 8 Metal mask having openings of 1 mm in length, 1 mm in width, and 100 ⁇ m in thickness at both ends of a copper wiring circuit (width 1 mm, length 50 mm, thickness 30 ⁇ m) formed on an alumina plate having a thickness of 1.2 mm
  • the paste-like silver particle composition of Example 1 was printed and applied in dots.
  • This alumina plate was placed in a gas flow furnace at room temperature, and as a reducing gas, a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume was used. The temperature was raised from room temperature to 300 ° C. at a heating rate of 1 ° C./second while flowing in minutes, held at 300 ° C.
  • a bump for circuit connection was manufactured.
  • the electric resistance between the electric circuit connecting bumps formed at both ends of the electric circuit was measured, it was less than 0.05 ⁇ , and the electric conductivity was sufficiently practical.
  • Example 9 Metal mask having openings of 1 mm in length, 1 mm in width, and 100 ⁇ m in thickness at both ends of a copper wiring circuit (width 1 mm, length 50 mm, thickness 30 ⁇ m) formed on an alumina plate having a thickness of 1.2 mm
  • the paste-like copper particle composition of Example 6 was printed and applied in dots.
  • This alumina plate was placed in a gas flow furnace at room temperature, and as a reducing gas, a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume was used. The temperature is raised from room temperature to 300 ° C. at a heating rate of 1 ° C./second while flowing in minutes, held at 300 ° C.
  • a bump for circuit connection was manufactured.
  • the electric resistance between the electric circuit connecting bumps formed at both ends of the electric circuit was measured, it was less than 0.1 ⁇ , and the electric conductivity was sufficiently practical.
  • Example 1 In Example 1, instead of the reducing gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume, nitrogen gas (the nitrogen gas concentration is 99.99% by volume or more) was used.
  • nitrogen gas the nitrogen gas concentration is 99.99% by volume or more
  • Example 2 In Example 1, instead of the reducing gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume, compressed air (nitrogen gas concentration is 78.0% by volume) was used. Under the same conditions as in Example 1, a specimen for hardness measurement and a specimen for joint strength measurement were prepared, and the hardness, the joint strength, and the oxidation of the copper substrate were measured and evaluated. 2 collectively.
  • Example 3 In Example 1, instead of the reducing gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume, a prepared gas having a nitrogen gas concentration of 98% by volume and an oxygen gas concentration of 2% by volume. A test body for hardness measurement and a test body for bonding strength measurement were prepared under the same conditions as in Example 1 except that the hardness, bonding strength, and oxidation of the copper substrate were measured and evaluated. The results are summarized in Table 2.
  • Example 4 Silver particles (shape: granular, average primary particle size: 1.0 ⁇ m, uncoated with water repellent organic matter) produced by a commercially available reduction method were introduced into a ball mill, and benzotriazole (Wako Pure Chemical Industries, Ltd.) The product is operated by adding an isopropyl alcohol solution (made by Reagent Grade 1), and dried to obtain flaky silver particles whose surface is coated with benzotriazole (average particle size of primary particles: 4.2 ⁇ m, hydrophilic organic substance) Benzotriazole amount: 0.5% by weight) was prepared.
  • a pasty silver particle composition was prepared under the same conditions as in Example 1 except that the benzotriazole-coated silver particles were used in place of the stearic acid-coated silver particles used in Example 1.
  • a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume is used to produce a specimen for hardness measurement and a specimen for bonding strength measurement in a gas flow furnace. did. These test specimens were measured and evaluated for hardness, bonding strength, and oxidation of the copper substrate, and the results are summarized in Table 2.
  • Example 5 In Example 1, instead of silver particles whose surface is coated with stearic acid, silver particles whose surface is not coated with a water-repellent organic material (shape: granular, average particle size of primary particles: 1.1 ⁇ m) are used. Except that, a paste-like silver particle composition was prepared under the same conditions. As a reducing gas, a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume was used to produce a specimen for hardness measurement and a specimen for bonding strength measurement in a gas flow furnace. . These test specimens were measured and evaluated for hardness, bonding strength, and oxidation of the copper substrate, and the results are summarized in Table 2.
  • Example 6 In Example 6, instead of the reducing gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume, compressed air (nitrogen gas concentration is 78.0% by volume) was used. Under the same conditions as in Example 6, a specimen for hardness measurement and a specimen for joint strength measurement were prepared, and the hardness, the joint strength, and the oxidation of the copper substrate were measured and evaluated. 2 collectively.
  • Example 7 In Example 6, instead of the reducing gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume, nitrogen gas (the nitrogen gas concentration is 99.99% by volume or more) was used.
  • nitrogen gas the nitrogen gas concentration is 99.99% by volume or more
  • Example 7 instead of the reducing gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume, compressed air (nitrogen gas concentration is 78.0% by volume) was used. Under the same conditions as in Example 7, a specimen for hardness measurement and a specimen for joint strength measurement were prepared, and the hardness, the joint strength, and the oxidation of the copper substrate were measured and evaluated. 2 collectively.
  • the metal member joining method of the present invention can strongly join metal members that are easily oxidized and corroded or discolored without being plasma-treated without being oxidized, capacitors, resistors, This is useful for bonding chip components such as diodes, memories, and arithmetic elements (CPUs) to substrates, and for radiating heat dissipation members.
  • the metal member assembly of the present invention is useful as an electronic component, an electronic device, an electrical component, an electrical device, or the like.
  • the method for manufacturing a bump for connecting an electric circuit of the present invention is useful for efficiently manufacturing a metal bump on a semiconductor element or a substrate.

Abstract

This invention provides a method for joining metallic members, characterized by comprising interposing a pasty metallic particle composition, comprising (A) heat sinterable metallic particles having an average particle diameter of more than 0.1 µm and not more than 50 µm and covered with a nonamine-type water repellent organic material and (B) a volatile dispersion medium, between a plurality of metallic members, heating the assembly in a reducing gas at a temperature of 70°C or above and 400°C or below to vaporize the volatile dispersion medium and thus to sinter the metallic particles, whereby the plurality of metallic members are joined to each other. There are also provided a metallic member joined product produced by using the joining method, and a method for manufacturing a bump for electric circuit connection.

Description

金属製部材の接合方法、金属製部材接合体、および、電気回路接続用バンプの製造方法Metal member joining method, metal member joined body, and method of manufacturing electric circuit connecting bump
本発明は、加熱焼結性金属粒子と揮発性分散媒とからなるペースト状金属粒子組成物を使用した金属製部材の接合方法、該接合方法を使用して得られる金属製部材接合体、および、電気回路接続用バンプの製造方法に関する。 The present invention relates to a method for joining metal members using a paste-like metal particle composition comprising heat-sinterable metal particles and a volatile dispersion medium, a metal member assembly obtained by using the joining method, and The present invention also relates to a method for manufacturing a bump for connecting an electric circuit.
銀、銅、ニッケルなどの金属粉末を液状熱硬化性樹脂組成物中に分散させてなる導電性・熱伝導性ペーストは、加熱により硬化して導電性・熱伝導性被膜が形成される。したがって、プリント回路基板上の導電性回路の形成、抵抗器やコンデンサ等の各種電子部品及び各種表示素子の電極の形成、電磁波シールド用導電性被膜の形成、コンデンサ、抵抗、ダイオード、メモリ、演算素子（ＣＰＵ）等のチップ部品の基板への接着、太陽電池の電極の形成、特に、アモルファスシリコン半導体を用いているために、高温処理のできない太陽電池の電極の形成、積層セラミックコンデンサ、積層セラミックインダクタ、積層セラミックアクチュエータ等のチップ型セラミック電子部品の外部電極の形成等に使用されている。 A conductive / thermal conductive paste obtained by dispersing a metal powder such as silver, copper, or nickel in a liquid thermosetting resin composition is cured by heating to form a conductive / thermal conductive film. Therefore, formation of conductive circuits on printed circuit boards, formation of various electronic components such as resistors and capacitors, and electrodes of various display elements, formation of conductive films for electromagnetic wave shielding, capacitors, resistors, diodes, memories, arithmetic elements (CPU) and other chip components to substrates, formation of solar cell electrodes, especially formation of solar cell electrodes that cannot be processed at high temperatures due to the use of amorphous silicon semiconductors, multilayer ceramic capacitors, multilayer ceramic inductors It is used for forming external electrodes of chip-type ceramic electronic components such as multilayer ceramic actuators.
近年、チップ部品の高性能化により、チップ部品からの発熱量が増え、電気伝導性はもとより、熱伝導性の向上が要求される。したがって、金属粒子の含有率を可能な限り増加することにより電気伝導性、熱伝導性を向上しようとする。ところが、そうすると、ペーストの粘度が上昇し、作業性が著しく低下するという問題がある。 2. Description of the Related Art In recent years, chip components have increased in performance, and the amount of heat generated from the chip components has increased, and improvement in thermal conductivity as well as electrical conductivity is required. Therefore, it tries to improve electrical conductivity and thermal conductivity by increasing the content of metal particles as much as possible. However, when it does so, there exists a problem that the viscosity of a paste rises and workability | operativity falls remarkably.
このような問題を解決するため、本発明者らは、銀粉末と揮発性分散媒とからなるペースト状銀組成物は、加熱すると当該揮発性分散媒が揮発し銀粉末が焼結して、極めて高い導電性と熱伝導性を有する固形状銀となること、および、金属製部材の接合や、導電回路の形成に有用なことを見出して国際出願した（WO2006/126614、WO2007/034833）。 In order to solve such a problem, the present inventors, when heated, the paste-like silver composition composed of silver powder and a volatile dispersion medium volatilizes the volatile dispersion medium and sinters the silver powder, An international application was made to find out that it was solid silver having extremely high electrical conductivity and thermal conductivity, and useful for joining metal members and forming conductive circuits (WO2006 / 126614, WO2007 / 034833).
しかしながら、銅または銅合金のような酸化しやすい部材を、焼結のため大気など酸素ガスを含むガス中において加熱した場合、銅または銅合金が酸化して腐食や変色してしまう問題がある。また、半導体素子上の電気回路接続用パッド部または基板上の電気回路接続用電極部が銅または銅合金のような酸化して腐食や変色がしやすい金属製であると、同様な問題がある。酸素ガスによる銅または銅合金の酸化を防ぐため、窒素ガスのような不活性ガス中において加熱した場合は、ペースト状銀組成物の焼結性や部材間の接合性が十分ではないという問題があることに、本発明者らは気付いた。 However, when an easily oxidized member such as copper or a copper alloy is heated in a gas containing oxygen gas such as the atmosphere for sintering, there is a problem that the copper or copper alloy is oxidized and corroded or discolored. In addition, if the electric circuit connecting pad portion on the semiconductor element or the electric circuit connecting electrode portion on the substrate is made of a metal which is easily oxidized and corroded or discolored, such as copper or a copper alloy, there is a similar problem. . In order to prevent oxidation of copper or copper alloy by oxygen gas, when heated in an inert gas such as nitrogen gas, there is a problem that the sinterability of the pasty silver composition and the bondability between members are not sufficient. To some extent, the present inventors have noticed.
特開2007-083288には、有機アミンで被覆された銅ペーストまたは銀ペーストを金属層（例、銅張積層板）と金属層（例、電子デバイスの電極）に塗布し、かつ、塗布面をプラズマ処理してから両者を密着させ還元性雰囲気中での加熱焼成により金属層同士を接合するという方法が開示されているが、煩雑な方法である。しかも、加熱焼成時に有機アミンが揮発して臭気や安全衛生上の問題が生じかねない。 In JP 2007-083288, a copper paste or silver paste coated with an organic amine is applied to a metal layer (eg, a copper clad laminate) and a metal layer (eg, an electrode of an electronic device), and the coated surface is A method is disclosed in which both metal layers are brought into close contact with each other after the plasma treatment, and the metal layers are bonded together by heating and firing in a reducing atmosphere, but this is a complicated method. In addition, organic amines may volatilize during heating and firing, which may cause odor and safety and health problems.
WO2006/126614WO2006 / 126614 WO2007/034833WO2007 / 034833 特開2007-083288号公報Japanese Unexamined Patent Publication No. 2007-083288
本発明者らは上記の問題点を解決するため鋭意研究した結果、ペースト状金属粒子組成物を酸化されやすい金属製部材間の接合剤に用いた場合でも、該金属製部材の酸化による腐食や変色がなく、かつ、金属粒子が十分に焼結して強固に接合する方法を見出した。本発明の目的は、ペースト状金属粒子組成物の焼結による金属製部材の接合において、プラズマ処理しなくても、該金属製部材を腐食や変色させることなく強固に接合する方法を提供することにあり、さらには金属製部材を腐食や変色させることなく強固に接合した金属製部材接合体を提供することにあり、さらには電気回路接続用パッド部または電気回路接続用電極部に強固に接合した電気回路接続用バンプを提供することにある。 As a result of diligent research to solve the above problems, the present inventors have found that even when the paste-like metal particle composition is used as a bonding agent between metal members that are easily oxidized, A method has been found in which there is no discoloration and the metal particles are sufficiently sintered and firmly bonded. An object of the present invention is to provide a method of strongly joining metal members without corrosion or discoloration without plasma treatment in joining of metal members by sintering a paste-like metal particle composition. Further, it is to provide a metal member joined body in which the metal member is firmly joined without being corroded or discolored, and further, firmly joined to the electric circuit connecting pad portion or the electric circuit connecting electrode portion. Another object of the present invention is to provide a bump for connecting an electric circuit.
この目的は、
「[1]　(A)平均粒径が０.１μｍより大きく５０μｍ以下であり非アミン系撥水性有機物で被覆された加熱焼結性金属粒子と、(B)揮発性分散媒とからなるペースト状金属粒子組成物を複数の金属製部材間に介在させ、還元性ガス中で７０℃以上４００℃以下での加熱により、該揮発性分散媒を揮散させ該金属粒子同士を焼結して複数の金属製部材同士を接合させることを特徴とする、金属製部材の接合方法。
[2]　還元性ガスが水素ガスまたは水素ガス含有ガスであることを特徴とする、[1]に記載の接合方法。
[3]　水素ガス含有ガスが水素ガスと不活性ガスの混合物であり、水素ガスの濃度が１～４０体積％であることを特徴とする、[2]に記載の接合方法。
[4]　非アミン系撥水性有機物が高・中級脂肪酸またはその誘導体であることを特徴とする、[1]に記載の接合方法。
[5]　高・中級脂肪酸は炭素原子数が６～２４であり、その誘導体が高・中級脂肪酸金属塩（アルカリ金属塩を除く）、高・中級脂肪酸アミドまたは高・中級脂肪酸エステルであることを特徴とする、[4]に記載の接合方法。
[6]　加熱焼結性金属粒子の金属が銀、銀合金、銅または銅合金であり、かつ、金属製部材の金属が銅、銀、金、白金、パラジウム、または、これら各金属の合金であることを特徴とする、[1]に記載の接合方法。
[7]　非アミン系撥水性有機物が高・中級脂肪酸またはその誘導体であり、加熱焼結性金属粒子の金属が銀、銀合金、銅または銅合金であり、かつ、金属製部材の金属が銅、銀、金、白金、パラジウム、または、これら各金属の合金であることを特徴とする、[1]に記載の接合方法。
[8]　還元性ガスが水素ガスまたは水素ガス含有ガスであり、非アミン系撥水性有機物が高・中級脂肪酸またはその誘導体であり、加熱焼結性金属粒子の金属が銀、銀合金、銅または銅合金であり、かつ、金属製部材の金属が銅、銀、金、白金、パラジウム、または、これら各金属の合金であることを特徴とする、[1]に記載の接合方法。
[9]　水素ガス含有ガスが水素ガスと不活性ガスの混合物であり、水素ガスの濃度が１～４０体積％であり、高・中級脂肪酸は炭素原子数が６～２４であり、その誘導体が高・中級脂肪酸金属塩（アルカリ金属塩を除く）、高・中級脂肪酸アミドまたは高・中級脂肪酸エステルであることを特徴とする、[8]に記載の接合方法。」により達成される。 This purpose is
“[1] (A) Paste form comprising heat-sinterable metal particles having an average particle size of more than 0.1 μm and not more than 50 μm and coated with a non-amine water-repellent organic substance, and (B) a volatile dispersion medium A metal particle composition is interposed between a plurality of metal members, and the volatile dispersion medium is volatilized by heating at 70 ° C. or more and 400 ° C. or less in a reducing gas to sinter the metal particles. A method for joining metal members, comprising joining metal members together.
[2] The joining method according to [1], wherein the reducing gas is hydrogen gas or a hydrogen gas-containing gas.
[3] The joining method according to [2], wherein the hydrogen gas-containing gas is a mixture of hydrogen gas and an inert gas, and the concentration of hydrogen gas is 1 to 40% by volume.
[4] The joining method according to [1], wherein the non-amine water-repellent organic substance is a high / intermediate fatty acid or a derivative thereof.
[5] The high / intermediate fatty acid has 6 to 24 carbon atoms, and the derivative is a high / intermediate fatty acid metal salt (excluding alkali metal salt), high / intermediate fatty acid amide or high / intermediate fatty acid ester. The joining method according to [4], which is characterized.
[6] The metal of the heat-sinterable metal particles is silver, silver alloy, copper or copper alloy, and the metal of the metal member is copper, silver, gold, platinum, palladium, or an alloy of each of these metals The joining method according to [1], characterized by comprising:
[7] The non-amine water-repellent organic substance is a high / intermediate fatty acid or a derivative thereof, the metal of the heat-sinterable metal particles is silver, a silver alloy, copper, or a copper alloy, and the metal of the metal member is copper Silver, gold, platinum, palladium, or an alloy of these metals, The joining method according to [1].
[8] The reducing gas is hydrogen gas or a hydrogen gas-containing gas, the non-amine water-repellent organic substance is a high / intermediate fatty acid or a derivative thereof, and the metal of the heat-sinterable metal particles is silver, silver alloy, copper or The joining method according to [1], which is a copper alloy, and the metal of the metal member is copper, silver, gold, platinum, palladium, or an alloy of these metals.
[9] The hydrogen gas-containing gas is a mixture of hydrogen gas and inert gas, the concentration of hydrogen gas is 1 to 40% by volume, the high / intermediate fatty acid has 6 to 24 carbon atoms, and its derivatives are The joining method according to [8], which is a high / intermediate fatty acid metal salt (excluding an alkali metal salt), a high / intermediate fatty acid amide, or a high / intermediate fatty acid ester. Is achieved.
また、この目的は、
「[10]　複数の金属製部材間で、平均粒径が０.１μｍより大きく５０μｍ以下であり非アミン系撥水性有機物で被覆された加熱焼結性金属粒子が、還元性ガス中で加熱焼結してなることを特徴とする、金属製部材接合体。

[11]　還元性ガスが水素ガスまたは水素ガス含有ガスであり、非アミン系撥水性有機物が高・中級脂肪酸またはその誘導体であり、加熱焼結性金属粒子の金属が銀、銀合金、銅または銅合金であり、かつ、金属製部材の金属が銅、銀、金、白金、パラジウム、または、これら各金属の合金であることを特徴とする、[10]に記載の金属製部材接合体。
[12]　水素ガス含有ガスが水素ガスと不活性ガスの混合物であり、水素ガスの濃度が１～４０体積％であり、高・中級脂肪酸は炭素原子数が６～２４であり、その誘導体が高・中級脂肪酸金属塩（アルカリ金属塩を除く）、高・中級脂肪酸アミドまたは高・中級脂肪酸エステルであることを特徴とする、[11]に記載の金属製部材接合体。」により達成される。
なお、上記金属製部材接合体は、上記接合方法を使用して、すなわち、[1]の「(A)平均粒径が０.１μｍより大きく５０μｍ以下であり非アミン系撥水性有機物で被覆された加熱焼結性金属粒子と、(B)揮発性分散媒とからなるペースト状金属粒子組成物を複数の金属製部材間に介在させ、還元性ガス中で７０℃以上４００℃以下での加熱により、該揮発性分散媒を揮散させ該金属粒子同士を焼結して複数の金属製部材同士を接合させることを特徴とする、金属製部材の接合方法。」という方法により、さらには[2]～[12]の方法により製造することができる。 This purpose is also
“[10] Heat-sinterable metal particles having an average particle size of more than 0.1 μm and less than 50 μm and coated with a non-amine water-repellent organic substance are heated and fired in a reducing gas. A metal member assembly, characterized by being formed by bonding.

[11] The reducing gas is hydrogen gas or a hydrogen gas-containing gas, the non-amine water-repellent organic substance is a high / intermediate fatty acid or a derivative thereof, and the metal of the heat-sinterable metal particles is silver, silver alloy, copper or The metal member assembly according to [10], which is a copper alloy, and the metal of the metal member is copper, silver, gold, platinum, palladium, or an alloy of these metals.
[12] The hydrogen gas-containing gas is a mixture of hydrogen gas and inert gas, the concentration of hydrogen gas is 1 to 40% by volume, the high / intermediate fatty acid has 6 to 24 carbon atoms, and its derivatives are The metal member assembly according to [11], which is a high / intermediate fatty acid metal salt (excluding alkali metal salts), a high / intermediate fatty acid amide, or a high / intermediate fatty acid ester. Is achieved.
The metal member bonded body is coated with the non-amine water-repellent organic material using the above bonding method, that is, “(A) The average particle diameter is larger than 0.1 μm and not larger than 50 μm in [1]. The paste-like metal particle composition comprising the heated sinterable metal particles and (B) the volatile dispersion medium is interposed between the plurality of metal members, and heated at 70 ° C. to 400 ° C. in a reducing gas. The metal member joining method is characterized in that the volatile dispersion medium is volatilized and the metal particles are sintered to join together a plurality of metal members. ] To [12].
また、この目的は、
「[13]　(A)平均粒径が０.１μｍより大きく５０μｍ以下であり非アミン系撥水性有機物で被覆された加熱焼結性金属粒子と、(B)揮発性分散媒とからなるペースト状金属粒子組成物を半導体素子上の電気回路接続用パッド部または基板上の電気回路接続用電極部にドット状に塗布し、還元性ガス中で７０℃以上４００℃以下での加熱により、該揮発性分散媒を揮散させ該金属粒子同士を焼結して、半導体素子上または基板上に金属粒子製バンプを形成することを特徴とする、電気回路接続用バンプの製造方法。
[14]　還元性ガスが水素ガスまたは水素ガス含有ガスであり、非アミン系撥水性有機物が高・中級脂肪酸またはその誘導体であり、加熱焼結性金属粒子の金属が銀、銀合金、銅または銅合金であり、かつ、電気回路接続用パッド部または基板上の電気回路接続用電極部の金属が銅、銀、金、白金、パラジウム、または、これら各金属の合金であることを特徴とする、[13]に記載の電気回路接続用バンプの製造方法。
[15]　水素ガス含有ガスが水素ガスと不活性ガスの混合物であり、水素ガスの濃度が１～４０体積％であり、高・中級脂肪酸は炭素原子数が６～２４であり、その誘導体が高・中級脂肪酸金属塩（アルカリ金属塩を除く）、高・中級脂肪酸アミドまたは高・中級脂肪酸エステルであることを特徴とする、[14]に記載の電気回路接続用バンプの製造方法。」により達成される。 This purpose is also
“[13] (A) Paste form comprising heat-sinterable metal particles having an average particle size of more than 0.1 μm and not more than 50 μm and coated with a non-amine water-repellent organic substance, and (B) a volatile dispersion medium The metal particle composition is applied in the form of dots on an electric circuit connecting pad on a semiconductor element or an electric circuit connecting electrode on a substrate, and the volatilization is effected by heating at 70 ° C. to 400 ° C. in a reducing gas. A method for producing a bump for connecting an electric circuit, comprising volatilizing a conductive dispersion medium and sintering the metal particles to form bumps made of metal particles on a semiconductor element or a substrate.
[14] The reducing gas is hydrogen gas or a hydrogen gas-containing gas, the non-amine water-repellent organic substance is a high / intermediate fatty acid or derivative thereof, and the metal of the heat-sinterable metal particles is silver, silver alloy, copper or It is a copper alloy, and the metal of the electric circuit connecting pad part or the electric circuit connecting electrode part on the substrate is copper, silver, gold, platinum, palladium, or an alloy of these metals. [13] A method for producing a bump for connecting an electric circuit according to [13].
[15] The hydrogen gas-containing gas is a mixture of hydrogen gas and inert gas, the concentration of hydrogen gas is 1 to 40% by volume, the high and intermediate fatty acids have 6 to 24 carbon atoms, and their derivatives are The method for producing a bump for connecting an electric circuit according to [14], which is a high / intermediate fatty acid metal salt (excluding an alkali metal salt), a high / intermediate fatty acid amide, or a high / intermediate fatty acid ester. Is achieved.
本発明の接合方法によると、酸化して腐食や変色がしやすい金属製部材間の接合であっても、ペースト状金属粒子組成物の加熱により該組成物中の揮発性分散媒が揮散し、該加熱焼結性金属粒子(A)同士が焼結して固体状となり、金属製部材が腐食や変色することなく強固に接合させることができる。
本発明の金属製部材接合体は、酸化して腐食や変色がしやすい金属製部材であっても、複数の金属製部材間で、平均粒径が０.１μｍより大きく５０μｍ以下であり非アミン系撥水性有機物で被覆された加熱焼結性金属粒子(A)が還元性ガス中で加熱焼結しているので、金属製部材が腐食や変色することなく強固に接合されている。
本発明の電気回路接続用バンプの製造方法によると、半導体素子上の電気回路接続用パッド部または基板上の電気回路接続用電極部が酸化して腐食や変色がしやすい金属製であっても、それらに強固に接合した金属粒子製バンプが形成される。 According to the joining method of the present invention, the volatile dispersion medium in the composition is volatilized by heating the paste-like metal particle composition even when joining between metal members that are easily oxidized and corroded or discolored. The heat-sinterable metal particles (A) are sintered and become solid, and the metal member can be firmly bonded without being corroded or discolored.
Even if the metal member assembly of the present invention is a metal member that is easily oxidized and corroded or discolored, the average particle diameter is larger than 0.1 μm and not more than 50 μm between the plurality of metal members. Since the heat-sinterable metal particles (A) coated with the water-repellent organic material are heat-sintered in a reducing gas, the metal members are firmly bonded without being corroded or discolored.
According to the method for manufacturing an electric circuit connecting bump of the present invention, even if the electric circuit connecting pad part on the semiconductor element or the electric circuit connecting electrode part on the substrate is oxidized and easily made corroded or discolored, A bump made of metal particles firmly bonded to them is formed.
実施例における接合強度測定用試験体Ａの平面図である。銅基板１上にペースト状銀粒子組成物２またはペースト状銅粒子組成物２をメタルマスクで印刷塗布し、銀チップ３または銅チップ３を搭載後、加熱して銀粒子または銅粒子を焼結し、銅基板１と銀チップ３または銅チップ３間の接合強度を測定するものである。It is a top view of the test body A for joint strength measurement in an Example. The paste-like silver particle composition 2 or the paste-like copper particle composition 2 is printed and applied on a copper substrate 1 with a metal mask, and the silver chip 3 or the copper chip 3 is mounted and then heated to sinter the silver particles or the copper particles. Then, the bonding strength between the copper substrate 1 and the silver chip 3 or the copper chip 3 is measured. 図１におけるＸ－Ｘ線断面図である。FIG. 2 is a sectional view taken along line XX in FIG.
符号の説明Explanation of symbols
Ａ　接合強度測定用試験体
１　銅基板
２　ペースト状銀粒子組成物またはペースト状銅粒子組成物（加熱焼結後は固体状銀または固体状銅）
３　銀チップまたは銅チップ A Test specimen for measuring bonding strength 1 Copper substrate 2 Paste-like silver particle composition or paste-like copper particle composition (solid silver or solid copper after heat sintering)
3 Silver chip or copper chip
本発明の接合方法は、(A) 平均粒径が０.１μｍより大きく５０μｍ以下であり非アミン系撥水性有機物で被覆された加熱焼結性金属粒子と、(B)揮発性分散媒とからなるペースト状金属粒子組成物を複数の金属製部材間に介在させ、還元性ガス中で、７０℃以上４００℃以下での加熱により該揮発性分散媒を揮散させ該金属粒子同士を焼結して複数の金属製部材同士を接合させることを特徴とする。 The joining method of the present invention comprises (A) heat-sinterable metal particles having a mean particle size of more than 0.1 μm and not more than 50 μm and coated with a non-amine water-repellent organic substance, and (B) a volatile dispersion medium. The paste-like metal particle composition is interposed between a plurality of metal members, and the volatile dispersion medium is volatilized by heating at 70 ° C. to 400 ° C. in a reducing gas to sinter the metal particles. A plurality of metal members are joined together.
加熱焼結性金属粒子(A)の平均粒径は０.１μｍより大きく５０μｍ以下である。この平均粒径は、レーザー回折散乱式粒度分布測定法により得られる一次粒子の平均粒径である。平均粒径が５０μｍを越えると、加熱焼結性金属粒子の焼結性が低下するため平均粒子径は小さい方が好ましい。このため２０μｍ以下であることが好ましく、特には１０μｍ以下であることが好ましい。しかし、平均粒径が０.１μｍ以下であると表面活性が強すぎて、ペースト状金属粒子組成物の保存安定性が低下し、加熱焼結時の接合強度が不均一になるため、平均粒径は０.１μｍより大きい。この観点から平均粒径は０.２μｍ以上であることが好ましい。すなわち、加熱焼結性金属粒子(A)の平均粒径範囲は０.２～１０μｍが好ましい。 The average particle size of the heat-sinterable metal particles (A) is larger than 0.1 μm and not larger than 50 μm. This average particle diameter is an average particle diameter of primary particles obtained by a laser diffraction / scattering particle size distribution measurement method. When the average particle diameter exceeds 50 μm, the sinterability of the heat-sinterable metal particles is lowered, so that the average particle diameter is preferably small. For this reason, it is preferable that it is 20 micrometers or less, and it is especially preferable that it is 10 micrometers or less. However, if the average particle size is 0.1 μm or less, the surface activity is too strong, the storage stability of the paste-like metal particle composition is lowered, and the bonding strength at the time of heat sintering becomes non-uniform. The diameter is greater than 0.1 μm. From this viewpoint, the average particle size is preferably 0.2 μm or more. That is, the average particle size range of the heat-sinterable metal particles (A) is preferably 0.2 to 10 μm.
加熱焼結性金属粒子の材質は、常温で固体であり、加熱により焼結しやすければよく、金、銀、銅、パラジウム、ニッケル、スズ、アルミニウム、および、これら各金属の合金が例示され、さらには金属化合物が例示される。
これらの材質のうちでは、加熱焼結性、焼結物の熱伝導性および導電性の点で、銀、銅、ニッケルが好ましく、銀、銀合金、銅、銅合金がより好ましく、銀または銅が特に好ましい。銀粒子は、表面または内部の一部が酸化銀または過酸化銀であってもよく、表面の全部が酸化銀または過酸化銀であってもよい。銅粒子は、表面または内部の一部が酸化銅であってもよく、表面の全部が酸化銅であってもよい。 The material of the heat-sinterable metal particles is solid at room temperature, and only needs to be easily sintered by heating. Gold, silver, copper, palladium, nickel, tin, aluminum, and alloys of these metals are exemplified. Furthermore, a metal compound is illustrated.
Among these materials, silver, copper, and nickel are preferable, silver, silver alloy, copper, and copper alloy are more preferable, and silver or copper is preferable in terms of heat-sinterability, thermal conductivity of the sintered product, and conductivity. Is particularly preferred. The silver particles may have a part of the surface or inside thereof that may be silver oxide or silver peroxide, and the entire surface may be silver oxide or silver peroxide. The copper particles may have copper oxide on the surface or part of the inside, or the entire surface may be copper oxide.
加熱焼結性金属粒子は、通常、単独の材質からなるが、複数の材質の粒子の混合物であってもよい。
加熱焼結性金属粒子は、それら加熱焼結性金属(例えば銀)により表面がメッキされた金属(例えば、銅、ニッケルまたはアルミニウム)粒子、それら加熱焼結性金属(例えば、銀)により表面がメッキされた樹脂（例えば、エポキシ樹脂、ポリエーテルサルフォン樹脂）粒子であってもよい。 The heat-sinterable metal particles are usually made of a single material, but may be a mixture of particles made of a plurality of materials.
Heat-sinterable metal particles are made of metal (for example, copper, nickel, or aluminum) particles whose surfaces are plated with the heat-sinterable metal (for example, silver), and the surface is made of the heat-sinterable metal (for example, silver). Plated resin (for example, epoxy resin, polyethersulfone resin) particles may be used.
加熱焼結性金属粒子の形状は、特に限定されず、球状、楕円球状、紡錘状、粒状、略立方体状、フレーク状、不定形状が例示される。その形状は、保存安定性の点で球状、粒状またはフレーク状が好ましい。好ましい加熱焼結性金属粒子は、還元法で作られた銀粒子、ならびに、還元法で作られた銅粒子である。
なお、還元法による銀粒子の製造方法は多く提案されており、通常、硝酸銀水溶液に水酸化ナトリウム水溶液を加えて酸化銀を調製し、これにホルマリンのような還元剤の水溶液を加えることにより酸化銀を還元して銀粒子分散液とし、分散液をろ過し、ろ過残渣を水洗し、乾燥をおこなうことにより製造される。また、還元法による銅粒子は、通常、硫酸銅水溶液とヒドラジン水溶液を接触反応させて銅粉を還元析出させ、純水で洗浄した後、乾燥して調製される（例えば、特開昭５９－１１６３０）。 The shape of the heat-sinterable metal particles is not particularly limited, and examples thereof include a spherical shape, an elliptical spherical shape, a spindle shape, a granular shape, a substantially cubic shape, a flake shape, and an indefinite shape. The shape is preferably spherical, granular or flaky from the viewpoint of storage stability. Preferred heat-sinterable metal particles are silver particles made by the reduction method and copper particles made by the reduction method.
Many methods for producing silver particles by the reduction method have been proposed. Usually, an aqueous solution of a reducing agent such as formalin is added to an aqueous solution of silver nitrate by adding an aqueous solution of sodium hydroxide to an aqueous solution of silver nitrate. It is produced by reducing silver to form a silver particle dispersion, filtering the dispersion, washing the filtration residue with water, and drying. The copper particles obtained by the reduction method are usually prepared by contact-reacting a copper sulfate aqueous solution and a hydrazine aqueous solution to reduce and precipitate copper powder, washing with pure water, and drying (see, for example, JP-A-59-59). 11630).
加熱焼結性金属粒子(A)は、加熱焼結性金属粒子の表面が非アミン系撥水性有機物で被覆ないし処理されている。該非アミン系撥水性有機物は潤滑性も優れていることが好ましく、高・中級脂肪酸、高・中級脂肪酸金属塩（ただし、アルカリ金属塩を除く）、高・中級脂肪酸アミドおよび高・中級脂肪酸エステルが例示される。被覆効果、処理効果の点で特には高・中級脂肪酸が好ましい。 In the heat-sinterable metal particles (A), the surface of the heat-sinterable metal particles is coated or treated with a non-amine water-repellent organic substance. The non-amine water-repellent organic material preferably has excellent lubricity, and includes high / intermediate fatty acids, high / intermediate fatty acid metal salts (excluding alkali metal salts), high / intermediate fatty acid amides and high / intermediate fatty acid esters. Illustrated. High and intermediate fatty acids are particularly preferred in terms of coating effect and treatment effect.
高級脂肪酸は、炭素原子数１５以上の脂肪酸であり、ペンタデカン酸、ヘキサデカン酸（パルミチン酸）、ヘプタデカン酸、オクタデカン酸（ステアリン酸）、１２－ヒドロキシオクタデカン酸（１２－ヒドロキシステアリン酸）、エイコサン酸（アラキン酸）、ドコサン酸（ベヘン酸）、テトラコサン酸（リグノセリン酸）、ヘキサコサン酸（セロチン酸）、オクタコサン酸（モンタン酸）等の直鎖飽和脂肪酸；２－ペンチルノナン酸、２－ヘキシルデカン酸、２－ヘプチルドデカン酸、イソステアリン酸等の分枝飽和脂肪酸；パルミトレイン酸、オレイン酸、イソオレイン酸、エライジン酸、リノール酸、リノレン酸、リシノール酸、ガドレン酸、エルカ酸、セラコレイン酸等の不飽和脂肪酸が例示される。 The higher fatty acid is a fatty acid having 15 or more carbon atoms, and includes pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), 12-hydroxyoctadecanoic acid (12-hydroxystearic acid), eicosanoic acid ( Linear saturated fatty acids such as arachidic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (serotic acid), octacosanoic acid (montanic acid); 2-pentylnonanoic acid, 2-hexyldecanoic acid, 2- Examples include branched saturated fatty acids such as heptyldodecanoic acid and isostearic acid; unsaturated fatty acids such as palmitoleic acid, oleic acid, isooleic acid, elaidic acid, linoleic acid, linolenic acid, ricinoleic acid, gadrenic acid, erucic acid, and ceracoleic acid The
中級脂肪酸は、炭素原子数が６～１４の脂肪酸であり、ヘキサン酸（カプロン酸）、ヘプタン酸、オクタン酸（カプリル酸）、ノナン酸（ペラルゴン酸）、デカン酸（カプリン酸）、ウンデカン酸、ドデカン酸（ラウリン酸）、トリデカン酸、テトラデカン酸（ミリスチン酸）等の直鎖飽和脂肪酸；イソヘキサン酸、イソヘプタン酸、２－エチルヘキサン酸、イソオクタン酸、イソノナン酸、２－プロピルヘプタン酸、イソデカン酸、イソウンデカン酸、２－ブチルオクタン酸、イソドデカン酸、イソトリデカン酸等の分枝飽和脂肪酸；１０－ウンデセン酸等の不飽和脂肪酸が例示される。 Intermediate fatty acids are fatty acids having 6 to 14 carbon atoms, such as hexanoic acid (caproic acid), heptanoic acid, octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, Linear saturated fatty acids such as dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid); isohexanoic acid, isoheptanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, 2-propylheptanoic acid, isodecanoic acid, Illustrative examples include branched saturated fatty acids such as isoundecanoic acid, 2-butyloctanoic acid, isododecanoic acid and isotridecanoic acid; and unsaturated fatty acids such as 10-undecenoic acid.
非アミン系撥水性有機物の被覆量は、金属粒子の粒径、比表面積、形状などにより変わるが、加熱焼結性金属粒子(A)の０.０１～３重量％が好ましく、０.１～２重量％がより好ましい。少なすぎると加熱焼結性金属粒子(A)が凝集しやすくなって保存安定性が低下し、ひいては加熱焼結時の接合強度が不均一になり、多すぎると加熱焼結性金属粒子(A)の加熱焼結性が低下するからである。 The coating amount of the non-amine water-repellent organic substance varies depending on the particle size, specific surface area, shape, etc. of the metal particles, but is preferably 0.01 to 3% by weight of the heat-sinterable metal particles (A), preferably 0.1 to 2% by weight is more preferred. If the amount is too small, the heat-sinterable metal particles (A) tend to agglomerate and the storage stability is lowered.As a result, the bonding strength at the time of heat-sintering becomes uneven, and if too large, the heat-sinterable metal particles (A) This is because the heat sinterability of) decreases.
非アミン系撥水性有機物の付着量は通常の方法で測定できる。例えば、窒素ガス中で非アミン系撥水性有機物の沸点以上に加熱して重量減少を測定する方法、加熱焼結性金属粒子(A)を酸素気流中で加熱して加熱焼結性金属粒子(A)に付着していた非アミン系撥水性有機物中の炭素を炭酸ガスに変え、赤外線吸収スペクトル法により定量分析する方法が例示される。 The adhesion amount of the non-amine water-repellent organic substance can be measured by a usual method. For example, a method of measuring weight loss by heating above the boiling point of a non-amine water-repellent organic substance in nitrogen gas, heating sinterable metal particles (A) in an oxygen stream and heating sinterable metal particles ( An example is a method in which carbon in the non-amine water-repellent organic material adhering to A) is changed to carbon dioxide and quantitative analysis is performed by infrared absorption spectroscopy.
非アミン系撥水性有機物が付着したフレーク状加熱焼結性金属粒子は、例えば、ボールミル中に球状のような形状の金属粒子と非アミン系撥水性有機物を投入して、ボールにより金属粒子を殴打することにより製造することができる（特公昭４０－６９７１、特開２０００－２３４１０７の[０００４]参照）。
具体的には、粒状の加熱焼結性金属粒子と、高・中級脂肪酸、高・中級脂肪酸金属塩（ただし、アルカリ金属塩を除く）、高・中級脂肪酸エステル、高・中級脂肪酸アミド等の非アミン系撥水性有機物とを、セラミック製のボールとともに、回転式ドラム装置（例えばボールミル）に投入し、ボールで金属粒子を殴打することにより、非アミン系撥水性有機物が付着したフレーク状加熱焼結性金属粒子を製造することができる。この際、潤滑性向上のための高・中級脂肪酸、高・中級脂肪酸金属塩（ただし、アルカリ金属塩を除く）、高・中級脂肪酸エステル、高・中級脂肪酸アミド等の非アミン系撥水性有機物が、フレーク状加熱焼結性金属粒子表面に付着する。 For example, flaky heat-sinterable metal particles with non-amine water-repellent organic substances adhered to them are placed in a ball mill with spherical metal particles and non-amine water-repellent organic substances, and the metal particles are beaten with balls. (See Japanese Patent Publication No. 40-6971, Japanese Patent Laid-Open No. 2000-234107, [0004]).
Specifically, granular heat-sinterable metal particles and high / intermediate fatty acids, high / intermediate fatty acid metal salts (excluding alkali metal salts), high / intermediate fatty acid esters, high / intermediate fatty acid amides, etc. Amine-based water-repellent organic materials are put together with ceramic balls into a rotary drum device (for example, a ball mill), and metal particles are beaten with the balls, so that flake-like heat-sintered with non-amine-based water-repellent organic materials attached. Metal particles can be produced. In this case, non-amine water-repellent organic substances such as high / intermediate fatty acids, high / intermediate fatty acid metal salts (except alkali metal salts), high / intermediate fatty acid esters, and high / intermediate fatty acid amides for improving lubricity And adheres to the surface of the flaky heat-sinterable metal particles.
加熱焼結性金属粒子(A)表面は、このような高・中級脂肪酸等により半分以上が被覆されておればよいが、全部が被覆されていることが好ましい。このように金属表面が非アミン系撥水性有機物により被覆された加熱焼結性金属粒子(A)は、撥水性を示す。
表面を非アミン系撥水性有機物で被覆した加熱焼結性金属粒子(A)は、非アミン系撥水性有機物の溶液中に加熱焼結性金属粒子を浸漬した後、該金属粒子を取り出して乾燥することにより製造することもできる。 The surface of the heat-sinterable metal particles (A) may be covered with more than half of such high / intermediate fatty acid, but it is preferable that the surface is covered entirely. Thus, the heat-sinterable metal particles (A) whose metal surface is coated with a non-amine water-repellent organic substance exhibit water repellency.
The heat-sinterable metal particles (A) whose surfaces are coated with a non-amine water-repellent organic substance are immersed in the solution of the non-amine-type water-repellent organic substance, and then the metal particles are taken out and dried. It can also be manufactured.
揮発性分散媒(B)は、粉状である金属粒子をペースト状にするために配合される。なお、ペースト状はクリーム状やスラリー状を含むものである。加熱時に加熱焼結性金属粒子が焼結可能とするため、あるいは、ペースト状金属粒子組成物を加熱による接合剤として使用可能にするためには、非揮発性ではなく、揮発性であることが必要である。特に、加熱焼結性金属粒子(A)が銀粒子や銅粒子の場合、焼結する際に分散媒が揮散すると、銀粒子や銅粒子が焼結しやすくなり、接合剤として利用しやすくなるからである。揮発性分散媒の沸点は、６０℃～３００℃であることが好ましい。沸点が６０℃未満であると、ペースト状金属粒子組成物を調製する作業中に溶媒が揮散しやすく、沸点が３００℃より大であると、加熱後も揮発性分散媒(B)が残留しかねないからである。 The volatile dispersion medium (B) is blended in order to make powdery metal particles into a paste. The paste form includes a cream form and a slurry form. In order to make the heat-sinterable metal particles sinterable during heating, or to make the paste-like metal particle composition usable as a bonding agent by heating, it must be volatile rather than non-volatile. is necessary. In particular, when the heat-sinterable metal particles (A) are silver particles or copper particles, if the dispersion medium is volatilized during sintering, the silver particles and copper particles are easily sintered and can be easily used as a bonding agent. Because. The boiling point of the volatile dispersion medium is preferably 60 ° C to 300 ° C. When the boiling point is less than 60 ° C., the solvent easily evaporates during the preparation of the paste-like metal particle composition, and when the boiling point is higher than 300 ° C., the volatile dispersion medium (B) remains even after heating. Because it might be.
そのような揮発性分散媒(B)は、炭素原子および水素原子からなる揮発性炭化水素化合物、炭素原子、水素原子および酸素原子からなる揮発性有機化合物、炭素原子、水素原子および窒素原子からなる揮発性有機化合物、炭素原子、水素原子、酸素原子および窒素原子からなる揮発性有機化合物、前記揮発性有機化合物のうちの親水性揮発性有機化合物と水との混合物などから選択される。これらはいずれも常温において液状である。
水は純水が好ましく、その電気伝導度は１００μS／ｃｍ以下が好ましく、１０μS／ｃｍ以下がより好ましい。純水の製造方法は、通常の方法で良く、イオン交換法、逆浸透法、蒸留法が例示される。 Such a volatile dispersion medium (B) is composed of a volatile hydrocarbon compound composed of carbon atoms and hydrogen atoms, a volatile organic compound composed of carbon atoms, hydrogen atoms and oxygen atoms, carbon atoms, hydrogen atoms and nitrogen atoms. It is selected from volatile organic compounds, volatile organic compounds composed of carbon atoms, hydrogen atoms, oxygen atoms and nitrogen atoms, a mixture of hydrophilic volatile organic compounds of the volatile organic compounds and water, and the like. These are all liquid at room temperature.
The water is preferably pure water, and its electric conductivity is preferably 100 μS / cm or less, more preferably 10 μS / cm or less. The pure water production method may be a normal method, and examples include an ion exchange method, a reverse osmosis method, and a distillation method.
具体的には、炭素原子、水素原子および酸素原子からなる揮発性有機化合物として、エチルアルコール、プロピルアルコール、ブチルアルコール、ペンチルアルコール、ヘキシルアルコール、ヘプチルアルコール、オクチルアルコール、ノニルアルコール、デシルアルコール等の揮発性一価アルコール；エチレングリコールモノメチルエーテル（メチルセロソルブ、メチルカルビトール）、エチレングリコールモノエチルエーテル（エメチルセロソルブ、エチルカルビトール）、エチレングリコールモノプロピルエーテル（プロピルセロソルブ、プロピルカルビトール）、エチレングリコールモノブチルエーテル（ブチルセロソルブ、ブチルカルビトール）、プロピレングリコールモノメチルエーテル、メチルメトキシブタノール等のエーテル結合を有する揮発性一価アルコール；ベンジルアルコール、２－フェニルエチルアルコールなどの揮発性アラルキルアルコール；エチレングリコール、プロピレングリコール、グリセリンなどの揮発性多価脂肪族アルコールが例示される。 Specifically, as volatile organic compounds composed of carbon atoms, hydrogen atoms and oxygen atoms, volatilization of ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, etc. Monohydric alcohol: ethylene glycol monomethyl ether (methyl cellosolve, methyl carbitol), ethylene glycol monoethyl ether (emethyl cellosolve, ethyl carbitol), ethylene glycol monopropyl ether (propyl cellosolve, propyl carbitol), ethylene glycol mono Ethers such as butyl ether (butyl cellosolve, butyl carbitol), propylene glycol monomethyl ether, methylmethoxybutanol Volatile monohydric alcohols having binding; benzyl alcohol, volatile aralkyl alcohols such as 2-phenylethyl alcohol, ethylene glycol, propylene glycol, volatile polyhydric aliphatic alcohols such as glycerin are exemplified.
さらにはアセトン、メチルエチルケトン、メチルイゾブチルケトン、シクロヘキサノン、ジアセトンアルコール（４－ヒドロキシ－４－メチル－２－ペンタノン）、２－オクタノン、イソホロン（３、５、５－トリメチル－２－シクロヘキセン－１－オン）、ジイブチルケトン（２、６－ジメチル－４－ヘプタノン）等の揮発性脂肪族ケトン；酢酸エチル（エチルアセテート）、酢酸ブチル、アセトキシエタン、酪酸メチル、ヘキサン酸メチル、オクタン酸メチル、デカン酸メチル、メチルセロソルブアセテート、プロピレングリコールモノメチルエーテルアセテートのような揮発性脂肪族カルボン酸エステル；テトラヒドロフラン、ジプロピルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジブチルエーテル、プロピレングリコールジメチルエーテル、エトキシエチルエーテル等の揮発性脂肪族エーテルが例示される。 Further, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), 2-octanone, isophorone (3, 5, 5-trimethyl-2-cyclohexene-1- ON), volatile aliphatic ketones such as dibutyl ketone (2,6-dimethyl-4-heptanone); ethyl acetate (ethyl acetate), butyl acetate, acetoxyethane, methyl butyrate, methyl hexanoate, methyl octoate, decane Volatile aliphatic carboxylic acid esters such as methyl acid, methyl cellosolve acetate, propylene glycol monomethyl ether acetate; tetrahydrofuran, dipropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene Glycol dibutyl ether, propylene glycol dimethyl ether, volatile aliphatic ethers such as ethoxyethyl ether, and the like.
炭素原子および水素原子からなる揮発性炭化水素化合物として、ｎ－パラフィン、イソパラフィン等の揮発性脂肪族炭化水素；トルエン、キシレン等の揮発性芳香族炭化水素が例示される。 Examples of volatile hydrocarbon compounds comprising carbon atoms and hydrogen atoms include volatile aliphatic hydrocarbons such as n-paraffins and isoparaffins; and volatile aromatic hydrocarbons such as toluene and xylene.
炭素原子、水素原子および窒素原子からなる揮発性有機化合物として、アセトニトリル、プロピオニトリルのような揮発性アルキルニトリルが例示される。
炭素原子、水素原子、酸素原子および窒素原子からなる揮発性有機化合物として、アセトアミド、N、N-ジメチルホルムアミドのような揮発性カルボン酸アミドが例示される。その他に、低分子量の揮発性シリコーンオイルおよび揮発性有機変成シリコーンオイルが例示される。 Examples of volatile organic compounds composed of carbon atoms, hydrogen atoms and nitrogen atoms include volatile alkyl nitriles such as acetonitrile and propionitrile.
Examples of volatile organic compounds composed of carbon atoms, hydrogen atoms, oxygen atoms and nitrogen atoms include volatile carboxylic acid amides such as acetamide and N, N-dimethylformamide. Other examples include low molecular weight volatile silicone oils and volatile organic modified silicone oils.
揮発性分散媒(B)の配合量は、加熱焼結性金属粒子(A)を常温においてペースト状にするのに十分な量である。加熱焼結性金属粒子(A)の粒径、表面積、形状など、および、揮発性分散媒(B)の種類、粘度などにより、ペースト状にするのに十分な量は変動するが、具体的には、例えば、加熱焼結性金属粒子(A)１００重量部当たり３～３０重量部である。
本発明で使用するペースト状金属粒子組成物には、本発明の目的に反しない限り、加熱焼結性金属粒子(A)以外の非金属系の粉体、金属化合物、金属錯体、チクソ剤、安定剤、着色剤等の添加物を少量ないし微量配合しても良い。 The blending amount of the volatile dispersion medium (B) is an amount sufficient to make the heat-sinterable metal particles (A) into a paste at room temperature. Depending on the particle size, surface area, shape, etc. of the heat-sinterable metal particles (A), and the type, viscosity, etc. of the volatile dispersion medium (B), the amount sufficient to make a paste varies, but the specific For example, the amount is 3 to 30 parts by weight per 100 parts by weight of the heat-sinterable metal particles (A).
In the paste-like metal particle composition used in the present invention, unless contrary to the object of the present invention, non-metallic powder other than the heat-sinterable metal particles (A), metal compound, metal complex, thixotropic agent, Additives such as stabilizers and colorants may be added in small amounts or in trace amounts.
本発明で使用するペースト状金属粒子組成物は、(A)平均粒径が０.１μｍより大きく５０μｍ以下であり非アミン系撥水性有機物で被覆された加熱焼結性金属粒子と、(B)揮発性分散媒を、ミキサーに投入し、均一なペースト状になるまで撹拌混合することにより、容易に製造することができる。 The paste-like metal particle composition used in the present invention comprises (A) a heat-sinterable metal particle having an average particle size of greater than 0.1 μm and 50 μm or less and coated with a non-amine water-repellent organic substance, and (B) The volatile dispersion medium can be easily manufactured by putting it into a mixer and stirring and mixing it until it becomes a uniform paste.
本発明で使用するペースト状金属粒子組成物は、加熱焼結性金属粒子(A)と揮発性分散媒(B)との混合物であり、常温でペースト状である。なお、ペースト状はクリーム状やスラリー状を含む。ペースト化することによりシリンダーやノズルから細い線状に吐出でき、また、メタルマスクによる印刷塗布が容易である。複数の金属製部材間に介在させるペースト状金属粒子組成物の厚さは、加熱焼結性金属粒子(A)の加熱焼結により必要な接合強度が発現する厚さであれば、特に限定されない。通常、５μｍ以上、１２００μｍ以下である。 The paste-like metal particle composition used in the present invention is a mixture of heat-sinterable metal particles (A) and a volatile dispersion medium (B), and is paste-like at room temperature. The paste form includes a cream form and a slurry form. By making it into a paste, it can be discharged in a thin line from a cylinder or nozzle, and printing with a metal mask is easy. The thickness of the paste-like metal particle composition interposed between a plurality of metal members is not particularly limited as long as the necessary bonding strength is exhibited by heat sintering of the heat sinterable metal particles (A). . Usually, it is 5 μm or more and 1200 μm or less.
本発明で使用する金属製部材は、塗布されたペースト状金属粒子組成物が加熱により該組成物中の揮発性分散媒が揮発し、加熱焼結性金属粒子同士(A)が焼結して接合する被接合体である。金属製部材の材質としては、金、銀、銅、白金、パラジウム、ニッケル、スズ、アルミニウム、および、これら各金属の合金が例示される。これらのうちでは導電性、接合性の点で、銅、銀、金、白金、パラジウム、または、これら各金属の合金が好ましい。金属製部材は前記金属でメッキされたものであってもよい。金属製部材としては、全体または一部が金属で形成されたリードフレーム、プリント基板、半導体チップ、放熱板が例示される。 In the metal member used in the present invention, the applied paste-like metal particle composition volatilizes the volatile dispersion medium in the composition by heating, and the heat-sinterable metal particles (A) sinter. It is a to-be-joined body to join. Examples of the material of the metal member include gold, silver, copper, platinum, palladium, nickel, tin, aluminum, and alloys of these metals. Among these, copper, silver, gold, platinum, palladium, or an alloy of these metals is preferable in terms of conductivity and bondability. The metal member may be plated with the metal. Examples of the metal member include a lead frame, a printed circuit board, a semiconductor chip, and a heat sink, all or part of which is made of metal.
本発明の接合方法は、上記ペースト状金属粒子組成物を複数の金属製部材間に介在させ、還元性ガス中で、７０℃以上４００℃以下での加熱により、該揮発性分散媒が揮散し該金属粒子同士が焼結して複数の金属製部材同士を接合する方法である。ペースト状金属粒子組成物を金属製部材間に介在させ、酸素ガスを含むガス中で加熱した場合は、金属製部材の酸化による腐食、変色等の問題がある。不活性ガス中で加熱した場合は、ペースト状金属粒子組成物中の金属粒子の焼結が十分でなく接合強度が低下するという問題がある。ところが、還元性ガス中で加熱した場合は、金属製部材の酸化による腐食、変色等の問題がなく、十分に焼結して接合強度が優れている。
なお、接合に使用するペースト状金属粒子組成物中の加熱焼結性金属粒子(A)用の加熱焼結性金属粒子と金属製部材の表面金属は、同一金属もしくは金属合金であることが好ましく、ついで、合金を形成しやすい金属同士であることが好ましい。 In the joining method of the present invention, the paste-like metal particle composition is interposed between a plurality of metal members, and the volatile dispersion medium is volatilized by heating at 70 ° C. or more and 400 ° C. or less in a reducing gas. In this method, the metal particles are sintered to join a plurality of metal members. When the paste-like metal particle composition is interposed between metal members and heated in a gas containing oxygen gas, there are problems such as corrosion and discoloration due to oxidation of the metal members. When heated in an inert gas, there is a problem that the metal particles in the paste-like metal particle composition are not sufficiently sintered and the bonding strength is lowered. However, when heated in a reducing gas, there is no problem of corrosion or discoloration due to oxidation of the metal member, and it is sufficiently sintered and has excellent bonding strength.
The heat-sinterable metal particles for heat-sinterable metal particles (A) in the paste-like metal particle composition used for joining and the surface metal of the metal member are preferably the same metal or metal alloy. Then, it is preferable that the metals are easy to form an alloy.
還元性ガスとして、水素ガス、一酸化炭素、アンモニア分解ガスが例示されるが、水素ガスが好ましい。還元性ガスは、純品である必要はなく、不活性ガスとの混合物であってもよい。不活性ガスとして、具体的には、ヘリウムガス、アルゴンガス、窒素ガスが例示され、特に窒素ガスが好ましい。 Examples of the reducing gas include hydrogen gas, carbon monoxide, and ammonia decomposition gas, but hydrogen gas is preferable. The reducing gas need not be a pure product, and may be a mixture with an inert gas. Specific examples of the inert gas include helium gas, argon gas, and nitrogen gas, and nitrogen gas is particularly preferable.
還元性ガスにおける還元性ガス成分と不活性ガス成分の比率は限定されないが、還元性ガス成分が水素ガスである場合は１～４０体積％であることがより好ましい。水素ガスの比率が１体積％未満であると、銅、銅合金などの酸化されやすい金属製部材の表面酸化物を還元して除去する効果が乏しく、また、ペースト状金属粒子組成物中の加熱焼結性金属粒子(A)の加熱焼結性が十分でなく接合強度が低下する。水素ガスの比率が４０体積％を越えると可燃性ガスとして取り扱い上の危険性が増すためである。最も好ましくは、水素ガスが５～１５体積％と窒素ガス９５～８５体積％とからなるフォーミングガスと称される還元性ガスである。 The ratio of the reducing gas component to the inert gas component in the reducing gas is not limited, but when the reducing gas component is hydrogen gas, it is more preferably 1 to 40% by volume. When the ratio of hydrogen gas is less than 1% by volume, the effect of reducing and removing the surface oxides of easily oxidized metal members such as copper and copper alloys is poor, and heating in the paste-like metal particle composition The sinterability of the sinterable metal particles (A) is not sufficient and the bonding strength is reduced. This is because if the ratio of hydrogen gas exceeds 40% by volume, the danger of handling as a combustible gas increases. Most preferably, the reducing gas is a reducing gas called a forming gas composed of 5 to 15% by volume of hydrogen gas and 95 to 85% by volume of nitrogen gas.
還元性ガスは、酸素ガスを含有しないことが望ましいが、含有するとしても金属製部材の酸化防止と危険防止のため少ないほど好ましく、特に１００ｐｐｍ以下であることが好ましい。このような還元性ガス中でペースト状金属粒子組成物を金属製部材間で加熱することにより、金属製部材が酸化による腐食や変色することなく、かつ、ペースト状金属粒子組成物中の加熱焼結性金属粒子(A)が十分に焼結して金属製部材を強固に接合することができる。 Although it is desirable that the reducing gas does not contain oxygen gas, even if it is contained, the reducing gas is preferably as small as possible in order to prevent oxidation and danger of the metal member, and particularly preferably 100 ppm or less. By heating the paste-like metal particle composition between metal members in such a reducing gas, the metal member does not corrode or discolor due to oxidation, and the paste-like metal particle composition is heated and fired in the paste-like metal particle composition. The cohesive metal particles (A) can be sufficiently sintered to firmly join the metal members.
本発明のペースト状金属粒子組成物は、加熱することにより揮発性分散媒が揮散する。本発明のペースト状金属粒子組成物は、加熱焼結性金属粒子(A)の焼結温度以上の温度に加熱することにより、揮発性分散媒(B)が揮散して、該金属粒子同士(A)が焼結し、導電性と熱伝導性が優れた固形状の金属となり金属製部材同士を接合する。ペースト状金属粒子組成物の加熱時に圧力や超音波振動を加えても良い。 When the paste-like metal particle composition of the present invention is heated, the volatile dispersion medium is volatilized. The paste-like metal particle composition of the present invention is heated to a temperature equal to or higher than the sintering temperature of the heat-sinterable metal particles (A), whereby the volatile dispersion medium (B) is volatilized, and the metal particles ( A) sinters and becomes a solid metal having excellent conductivity and thermal conductivity, and joins metal members together. Pressure or ultrasonic vibration may be applied during the heating of the paste-like metal particle composition.
この際、揮発性分散媒(B)が揮散し、ついで加熱焼結性金属粒子(A)同士が焼結してもよく、揮発性分散媒(B)の揮散と共に加熱焼結性金属粒子(A)同士が焼結してもよい。特に加熱焼結性金属粒子(A)が銀粒子の場合は、銀が本来大きな強度と極めて高い電気伝導性と熱伝導性を有するため、銀粒子同士の焼結物も、大きな強度ときわめて高い電気伝導性と熱伝導性を有する。加熱焼結性金属粒子(A)が銅粒子の場合は、銅が本来極めて高い電気伝導性と熱伝導性を有するため、銅粒子同士の焼結物も、きわめて高い電気伝導性と熱伝導性を有する。 At this time, the volatile dispersion medium (B) is volatilized, and then the heat-sinterable metal particles (A) may be sintered together, and with the volatilization of the volatile dispersion medium (B), the heat-sinterable metal particles ( A) may be sintered together. In particular, when the heat-sinterable metal particles (A) are silver particles, since silver has inherently high strength and extremely high electrical and thermal conductivity, the sintered product of silver particles also has high strength and extremely high. It has electrical conductivity and thermal conductivity. When the heat-sinterable metal particles (A) are copper particles, copper originally has extremely high electrical and thermal conductivity, so the sintered product of copper particles also has extremely high electrical and thermal conductivity. Have
この際の加熱温度は、揮発性分散媒(B)が揮散し、加熱焼結性金属粒子(A)が焼結できる温度であればよく、通常７０℃以上であり、１５０℃以上がより好ましい。しかし、４００℃を越えると揮発性分散媒が突沸的に蒸発して、固形状金属の形状に悪影響が出る可能性があるため、４００℃以下であることが必要であり、より好ましくは３００℃以下である。 The heating temperature at this time may be a temperature at which the volatile dispersion medium (B) is volatilized and the heat-sinterable metal particles (A) can be sintered, and is usually 70 ° C. or higher, and more preferably 150 ° C. or higher. . However, if the temperature exceeds 400 ° C., the volatile dispersion medium may suddenly evaporate and the shape of the solid metal may be adversely affected. Therefore, the temperature must be 400 ° C. or less, more preferably 300 ° C. It is as follows.
本発明で使用するペースト状金属粒子組成物は、加熱により揮発性分散媒(B)が揮散し、加熱焼結性金属粒子(A)同士が焼結する。複数の金属製部材間の接合に用いた場合、接触していた金属製部材、例えば金メッキ基板、銀基板、銀メッキ金属基板、銅基板、アルミニウム基板、ニッケルメッキ基板、スズメッキ金属基板等の金属系基板へ強固に接着し、電気絶縁性基板上の電極等金属部分へ強固に接着するので、本発明の接合方法は、金属系基板や金属部分を有する電子部品、電子装置、電気部品、電気装置等の接合に有用である。 In the paste-like metal particle composition used in the present invention, the volatile dispersion medium (B) is volatilized by heating, and the heat-sinterable metal particles (A) are sintered together. When used for joining between a plurality of metal members, the metal members that were in contact, such as a gold-plated substrate, silver substrate, silver-plated metal substrate, copper substrate, aluminum substrate, nickel-plated substrate, tin-plated metal substrate, etc. Since it adheres firmly to a substrate and firmly adheres to a metal part such as an electrode on an electrically insulating substrate, the bonding method of the present invention is an electronic component, an electronic device, an electrical component, and an electrical device having a metal substrate and a metal part. It is useful for joining such as.
そのような接合として、コンデンサ、抵抗等のチップ部品と回路基板との接合、ダイオード、メモリ、ＩＣ、ＣＰＵ等の半導体チップとリードフレームもしくは回路基板との接合、高発熱のＣＰＵチップと冷却板との接合が例示される。 Such bonding includes bonding of chip parts such as capacitors and resistors and circuit boards, bonding of semiconductor chips such as diodes, memories, ICs, and CPUs to lead frames or circuit boards, and high-heat generation CPU chips and cooling plates. Are exemplified.
本発明の金属製部材接合体は、複数の金属製部材間で、平均粒径が０.１μｍより大きく５０μｍ以下であり非アミン系撥水性有機物で被覆された加熱焼結性金属粒子が、還元性ガス中で加熱焼結してなることを特徴とする。
金属製部材、平均粒径が０.１μｍより大きく５０μｍ以下であり非アミン系撥水性有機物で被覆された加熱焼結性金属粒子、還元性ガス、加熱焼結については、金属製部材の接合方法に関して説明したとおりである。複数の金属製部材間に介在している加熱焼結した金属層の厚さは、必要な接合強度が発現する厚さであれば、特に限定されない。通常、３μｍ以上、１０００μｍ以下である。 In the metal member joined body of the present invention, the heat-sinterable metal particles coated with a non-amine water-repellent organic substance having an average particle size of more than 0.1 μm and 50 μm or less are reduced between a plurality of metal members. It is characterized by being heated and sintered in a reactive gas.
Metal member, heat sinterable metal particles having an average particle size greater than 0.1 μm and less than 50 μm and coated with a non-amine water-repellent organic substance, reducing gas, and heat sintering Is as described above. The thickness of the heat-sintered metal layer interposed between the plurality of metal members is not particularly limited as long as the necessary bond strength is exhibited. Usually, it is 3 μm or more and 1000 μm or less.
本発明の金属製部材接合体は、酸化して腐食や変色がしやすい金属製部材であっても、複数の金属製部材間が、平均粒径が０.１μｍより大きく５０μｍ以下であり非アミン系撥水性有機物で被覆された加熱焼結性金属粒子が還元性ガス中で加熱焼結しているので、金属製部材が腐食や変色することなく強固に接合している。
そのような金属製部材接合体として、コンデンサ、抵抗等のチップ部品と回路基板との接合体、ダイオード、メモリ、ＩＣ、ＣＰＵ等の半導体チップとリードフレームもしくは回路基板との接合体、高発熱のＣＰＵチップと冷却板との接合体が例示される。 Even if the metal member assembly of the present invention is a metal member which is easily oxidized and corroded or discolored, the average particle size is between 0.1 μm and 50 μm or less between the plurality of metal members. Since the heat-sinterable metal particles coated with the water-repellent organic material are heat-sintered in a reducing gas, the metal member is firmly bonded without being corroded or discolored.
As such a metal member joined body, a joined body of a chip component such as a capacitor or a resistor and a circuit board, a joined body of a semiconductor chip such as a diode, memory, IC, or CPU and a lead frame or a circuit board, a high heat generating body A joined body of a CPU chip and a cooling plate is exemplified.
本発明で使用するペースト状金属粒子組成物は、加熱により揮発性分散媒(B)が揮散し、加熱焼結性金属粒子(A)同士が焼結する。半導体素子上の電気回路接続用パッド部または基板上の電気回路接続用端部にドット状に塗布して加熱することにより、該揮発性分散媒を揮散させ当該金属粒子同士を焼結して、半導体素子上または基板上に金属製バンプを製造することができる。 In the paste-like metal particle composition used in the present invention, the volatile dispersion medium (B) is volatilized by heating, and the heat-sinterable metal particles (A) are sintered together. By applying and heating the electrical circuit connection pad on the semiconductor element or the electrical circuit connection end on the substrate in the form of dots, the volatile dispersion medium is volatilized and the metal particles are sintered together, Metal bumps can be manufactured on a semiconductor element or substrate.
本発明の実施例と比較例を掲げる。実施例と比較例中、部と記載されているのは、重量部を意味する。ペースト状金属粒子組成物中の加熱焼結性金属粒子(A)の焼結後の硬さ、ペースト状金属粒子組成物による金属製部材として銅の接合強度、接合後の金属製部材として銅の酸化、および、ガス中の酸素濃度は下記のとおり測定、評価した。なお、特に記載のない場合の温度は２３℃である。 Examples and comparative examples of the present invention will be given. In the examples and comparative examples, “parts” means “parts by weight”. The hardness after sintering of the heat-sinterable metal particles (A) in the paste-like metal particle composition, the bonding strength of copper as the metal member by the paste-like metal particle composition, and the copper as the metal member after bonding Oxidation and oxygen concentration in the gas were measured and evaluated as follows. In addition, the temperature in case there is no description in particular is 23 degreeC.
［硬さ］
ポリテトラフルオロエチレン樹脂板上に１５ｍｍ角の開口部を有する厚さ１ｍｍのステンレス製のマスクを置き、ペースト状金属粒子組成物を印刷塗布した。室温のガス流通炉に入れガス置換後、ガスを流量１リットル／分で流しながら室温から昇温速度１℃／秒で３００℃まで昇温し、３００℃で１時間保持後、室温まで冷却してペースト状金属粒子組成物中の金属粒子を焼結した。焼結物をポリテトラフルオロエチレン樹脂板からはずして硬さ測定用試験体とした。ＪＩＳ　Ｚ２２４４（ビッカース硬さ試験）に準拠して硬さを２個測定し、その平均値を硬さと測定した。 [Hardness]
A 1 mm thick stainless steel mask having a 15 mm square opening was placed on the polytetrafluoroethylene resin plate, and the paste-like metal particle composition was applied by printing. After replacing the gas in a room-temperature gas flow furnace, the temperature was raised from room temperature to 300 ° C. at a heating rate of 1 ° C./second while flowing the gas at a flow rate of 1 liter / minute, held at 300 ° C. for 1 hour, and then cooled to room temperature. The metal particles in the paste-like metal particle composition were sintered. The sintered product was removed from the polytetrafluoroethylene resin plate to obtain a specimen for hardness measurement. Two hardnesses were measured according to JIS Z2244 (Vickers hardness test), and the average value was measured as hardness.
［接合強度］
幅２５ｍｍ×長さ７０ｍｍ、厚さ１.０ｍｍの銅基板（無酸素銅製）上に、１０ｍｍの間隔をおいて４つの開口部（２.５ｍｍ×２.５ｍｍ）を有する１００μｍ厚のメタルマスクを用いて、ペースト状金属粒子組成物を印刷塗布し、該ペースト状金属粒子組成物中の金属粒子が銀粒子の場合は、その上にサイズが２.５ｍｍ×２.５ｍｍ×０.５ｍｍの銀チップ（銀純度９９.９９％）を、該ペースト状金属粒子組成物中の金属粒子が銅粒子の場合は、その上にサイズが２.５ｍｍ×２.５ｍｍ×０.５ｍｍの銅チップ（無酸素銅製）を搭載した。該銀チップまたは該銅チップを搭載した銅基板を室温のガス流通炉に入れ、空気を所定のガスに置換後、所定のガスを流量１リットル／分で流しながら室温から昇温速度１℃／秒で３００℃まで昇温し、３００℃で１時間保持後、室温まで冷却して接合した。 [Joint strength]
A 100 μm-thick metal mask having four openings (2.5 mm × 2.5 mm) at an interval of 10 mm on a copper substrate (made of oxygen-free copper) having a width of 25 mm × length of 70 mm and a thickness of 1.0 mm. In the case where the paste-like metal particle composition is printed and applied, and the metal particles in the paste-like metal particle composition are silver particles, silver having a size of 2.5 mm × 2.5 mm × 0.5 mm is formed thereon. When the metal particles in the paste-like metal particle composition are copper particles, a chip having a size of 2.5 mm × 2.5 mm × 0.5 mm is used on the chip (silver purity 99.99%). (Made of oxygen copper). The silver chip or the copper substrate on which the copper chip is mounted is placed in a gas flow furnace at room temperature, air is replaced with a predetermined gas, and a temperature rising rate from room temperature is 1 ° C./minute while flowing a predetermined gas at a flow rate of 1 liter / min. The temperature was raised to 300 ° C. in seconds, held at 300 ° C. for 1 hour, then cooled to room temperature and joined.
かくして得られた接合強度測定用試験体を接着強さ試験機の試験体取付け具にセットし、該銀チップまたは銅チップの側面を接着強さ試験機の押圧棒により押厚速度２３ｍｍ／分で押圧し、接合部がせん断破壊したときの荷重をもって接着強さ（単位；Ｎ（ｋｇｆ））とした。４個の接着強さの平均値を接合強度とした。 The test specimen for bonding strength measurement thus obtained was set on a test specimen fixture of an adhesive strength tester, and the side surface of the silver chip or copper chip was pressed with a pressing bar of the adhesive strength tester at a thickness rate of 23 mm / min. The adhesive strength (unit: N (kgf)) was determined by the load when the joint was sheared and pressed. The average value of the four bond strengths was defined as the bond strength.
［銅の酸化］
目視により、接合強度測定用試験体の銅基板および銅チップと、試験体作成用の銅基板および銅チップとを比較観察して、色の変化で評価した。 [Oxidation of copper]
By visual observation, the copper substrate and the copper chip of the test body for bonding strength measurement were compared with the copper substrate and the copper chip for preparing the test body, and the color change was evaluated.
［酸素ガス濃度］
加熱焼結時の雰囲気中の酸素ガス濃度を、酸素濃度計（東レエンジニアリング株式会社製、ＫＦ－４００）により測定した。 [Oxygen gas concentration]
The oxygen gas concentration in the atmosphere during heating and sintering was measured with an oxygen concentration meter (KF-400, manufactured by Toray Engineering Co., Ltd.).
[実施例１]
市販の、還元法で製造され表面がステアリン酸で被覆された銀粒子（形状：粒状、１次粒子の平均粒径：１.１μｍ、非アミン系撥水性有機物であるステアリン酸量：０.３重量％）１００部に、揮発性分散媒として酢酸２－（２ブトキシエトキシ）エタン（和光純薬工業株式会社製、試薬１級）８部を添加し、ヘラを用いて均一に混合することによりペースト状銀粒子組成物を調製した。 [Example 1]
Commercially available silver particles produced by a reduction method and coated on the surface with stearic acid (shape: granular, average particle size of primary particles: 1.1 μm, amount of stearic acid as non-amine water-repellent organic substance: 0.3 By adding 8 parts of 2- (2butoxyethoxy) ethane acetate (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade 1) as a volatile dispersion medium to 100 parts by weight and mixing uniformly with a spatula A pasty silver particle composition was prepared.
還元性ガスとして、水素ガス濃度が１０体積％であり窒素ガス濃度が９０体積％である混合ガスを用い、ガス流通炉内で硬さ測定用の試験体および接合強度測定用の試験体を作製した。これらの試験体について、硬さ、接合強度、および、銅基板の酸化の測定、評価をし、結果を表１にまとめて示した。以上の結果より、この接合方法が、ペースト状銀粒子組成物中の銀粒子を強固に焼結し、銅基板と銀チップを酸化することなく強固に接合するのに有用なことがわかった。 As a reducing gas, a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume is used to produce a specimen for hardness measurement and a specimen for bonding strength measurement in a gas flow furnace. did. These test specimens were measured and evaluated for hardness, bonding strength, and oxidation of the copper substrate, and the results are summarized in Table 1. From the above results, it was found that this joining method is useful for strongly sintering the silver particles in the paste-like silver particle composition and strongly joining the copper substrate and the silver chip without being oxidized.
[実施例２]
ボールミルに、市販の還元法で製造された銀粒子（形状：粒状、１次粒子の平均粒径：１.０μｍ、非アミン系撥水性有機物による被覆なし）を投入し、オレイン酸を添加して稼働することにより、表面がオレイン酸で被覆されたフレーク状銀粒子（１次粒子の平均粒径：３.０μｍ、非アミン系撥水性有機物であるオレイン酸量：０.３重量％）を調製した。 [Example 2]
Into a ball mill, silver particles (shape: granular, average primary particle size: 1.0 μm, uncoated with non-amine water-repellent organic substance) produced by a commercially available reduction method are added, and oleic acid is added. By operation, flaky silver particles whose surfaces are coated with oleic acid (average particle size of primary particles: 3.0 μm, oleic acid amount of non-amine water-repellent organic substance: 0.3% by weight) are prepared. did.
実施例１において用いた銀粒子の代わりに、上記フレーク状銀粒子を用いたほかは、実施例１と同様の条件でペースト状銀粒子組成物を調製した。
還元性ガスとして、水素ガス濃度が１０体積％であり窒素ガス濃度が９０体積％である混合ガスを用い、ガス流通炉内で硬さ測定用の試験体および接合強度測定用の試験体を作製した。これらの試験体について、硬さ、接合強度、および、銅基板の酸化の測定、評価をし、結果を表１にまとめて示した。以上の結果より、この接合方法が、ペースト状銀粒子組成物中の銀粒子を強固に焼結し、銅基板と銀チップを酸化することなく強固に接合するのに有用なことがわかった。 A pasty silver particle composition was prepared under the same conditions as in Example 1 except that the flaky silver particles were used in place of the silver particles used in Example 1.
As a reducing gas, a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume is used to produce a specimen for hardness measurement and a specimen for bonding strength measurement in a gas flow furnace. did. These test specimens were measured and evaluated for hardness, bonding strength, and oxidation of the copper substrate, and the results are summarized in Table 1. From the above results, it was found that this joining method is useful for strongly sintering the silver particles in the paste-like silver particle composition and strongly joining the copper substrate and the silver chip without being oxidized.
[実施例３]
実施例１において、還元性ガスとして、水素ガス濃度が１０体積％であり窒素ガス濃度が９０体積％である混合ガスの代わりに、水素ガス濃度が５体積％であり窒素ガス濃度が９５体積％である混合ガスを用いた以外は、実施例１と同様の条件で、硬さ測定用の試験体および接合強度測定用の試験体を作製し、硬さ、接合強度、および、銅基板の酸化の測定、評価をし、結果を表１にまとめて示した。以上の結果より、この接合方法がペースト状銀粒子組成物中の銀粒子を強固に焼結し、銅基板と銀チップを酸化することなく強固に接合するのに有用なことがわかった。 [Example 3]
In Example 1, as the reducing gas, instead of the mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume, the hydrogen gas concentration is 5% by volume and the nitrogen gas concentration is 95% by volume. A test specimen for hardness measurement and a test specimen for joint strength measurement were prepared under the same conditions as in Example 1 except that a mixed gas was used. Hardness, joint strength, and oxidation of the copper substrate Were measured and evaluated, and the results are summarized in Table 1. From the above results, it was found that this joining method is useful for strongly sintering the silver particles in the paste-like silver particle composition and strongly joining the copper substrate and the silver chip without being oxidized.
[実施例４]
実施例１において、還元性ガスとして、水素ガス濃度が１０体積％であり窒素ガス濃度が９０体積％である混合ガスの代わりに、水素ガス濃度が２０体積％であり窒素ガス濃度が８０体積％である混合ガスを用いた以外は実施例１と同様の条件で、硬さ測定用の試験体および接合強度測定用の試験体を作製し、硬さ、接合強度、および、銅基板の酸化の測定、評価をし、結果を表１にまとめて示した。以上の結果より、この接合方法がペースト状銀粒子組成物中の銀粒子を強固に焼結し、銅基板と銀チップを酸化することなく強固に接合するのに有用なことがわかった。 [Example 4]
In Example 1, as a reducing gas, instead of a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume, the hydrogen gas concentration is 20% by volume and the nitrogen gas concentration is 80% by volume. A test specimen for hardness measurement and a test specimen for bonding strength measurement were prepared under the same conditions as in Example 1 except that a mixed gas was used, and the hardness, bonding strength, and oxidation of the copper substrate were measured. Measurement and evaluation were performed, and the results are summarized in Table 1. From the above results, it was found that this joining method is useful for strongly sintering the silver particles in the paste-like silver particle composition and strongly joining the copper substrate and the silver chip without being oxidized.
[実施例５]
実施例１で使用したステアリン酸被覆銀粒子の代わりに、還元法で製造され表面がラウリン酸で被覆された銀粒子（形状：粒状、１次粒子の平均粒径：１.１μｍ、非アミン系撥水性有機物であるラウリン酸量：０.２重量％）を用いたほかは、実施例１と同様の条件でペースト状銀粒子組成物を調製した。 [Example 5]
Instead of the stearic acid-coated silver particles used in Example 1, silver particles produced by the reduction method and coated on the surface with lauric acid (shape: granular, average particle diameter of primary particles: 1.1 μm, non-amine system) A paste-like silver particle composition was prepared under the same conditions as in Example 1 except that the water-repellent organic substance lauric acid amount: 0.2 wt% was used.
還元性ガスとして、水素ガス濃度が１０体積％であり窒素ガス濃度が９０体積％である混合ガスを用い、ガス流通炉内で硬さ測定用の試験体および接合強度測定用の試験体を作製した。これらの試験体について、硬さ、接合強度、および、銅基板の酸化の測定、評価をし、結果を表１にまとめて示した。以上の結果より、この接合方法が、ペースト状銀粒子組成物中の銀粒子を強固に焼結し、銅基板と銀チップを酸化することなく強固に接合するのに有用なことがわかった。 As a reducing gas, a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume is used to produce a specimen for hardness measurement and a specimen for bonding strength measurement in a gas flow furnace. did. These test specimens were measured and evaluated for hardness, bonding strength, and oxidation of the copper substrate, and the results are summarized in Table 1. From the above results, it was found that this joining method is useful for strongly sintering the silver particles in the paste-like silver particle composition and strongly joining the copper substrate and the silver chip without being oxidized.
［実施例６］
市販の、還元法で製造され表面がステアリン酸で被覆された銅粒子（形状：粒状、１次粒子の平均粒径：１.１μｍ、非アミン系撥水性有機物であるステアリン酸量：０.３重量％）１００部に、揮発性分散媒として酢酸２－（２ブトキシエトキシ）エタン（和光純薬工業株式会社製、試薬１級）８部を添加し、ヘラを用いて均一に混合することによりペースト状銅粒子組成物を調製した。 [Example 6]
Commercially available copper particles manufactured by the reduction method and coated with stearic acid on the surface (shape: granular, average particle size of primary particles: 1.1 μm, amount of stearic acid as non-amine water-repellent organic substance: 0.3 By adding 8 parts of 2- (2butoxyethoxy) ethane acetate (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade 1) as a volatile dispersion medium to 100 parts by weight and mixing uniformly with a spatula A paste-like copper particle composition was prepared.
還元性ガスとして、水素ガス濃度が１０体積％であり窒素ガス濃度が９０体積％である混合ガスを用い、ガス流通炉内で硬さ測定用の試験体および接合強度測定用の試験体を作製した。これらの試験体について、硬さ、接合強度、および、銅基板と銅チップの酸化の測定、評価をし、結果を表１にまとめて示した。以上の結果より、この接合方法が、ペースト状銅粒子組成物中の銅粒子を強固に焼結し、銅基板と銅チップを酸化することなく強固に接合するのに有用なことがわかった。 As a reducing gas, a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume is used to produce a specimen for hardness measurement and a specimen for bonding strength measurement in a gas flow furnace. did. These test specimens were measured and evaluated for hardness, bonding strength, and oxidation of the copper substrate and the copper chip, and the results are shown in Table 1. From the above results, it has been found that this joining method is useful for strongly sintering the copper particles in the paste-like copper particle composition and strongly joining the copper substrate and the copper chip without being oxidized.
［実施例７］
ボールミルに、市販の還元法で製造された銅粒子（形状：粒状、１次粒子の平均粒径：１.０μｍ、非アミン系撥水性有機物による被覆なし）を投入し、オレイン酸を添加して稼働することにより、表面がオレイン酸で被覆されたフレーク状銅粒子（１次粒子の平均粒径：３.０μｍ、非アミン系撥水性有機物であるオレイン酸量：０.３重量％）を調製した。 [Example 7]
Copper particles (shape: granular, average particle size of primary particles: 1.0 μm, uncoated with non-amine water-repellent organic substance) produced by a commercially available reduction method are put into a ball mill, and oleic acid is added. By operating, flaky copper particles whose surface is coated with oleic acid (average particle size of primary particles: 3.0 μm, oleic acid amount of non-amine water-repellent organic substance: 0.3% by weight) are prepared. did.
実施例６において用いた銅粒子の代わりに、上記フレーク状銅粒子を用いたほかは、実施例６と同様の条件でペースト状銅粒子組成物を調製した。
還元性ガスとして、水素ガス濃度が１０体積％であり窒素ガス濃度が９０体積％である混合ガスを用い、ガス流通炉内で硬さ測定用の試験体および接合強度測定用の試験体を作製した。これらの試験体について、硬さ、接合強度、および、銅基板と銅チップの酸化の測定、評価をし、結果を表１にまとめて示した。以上の結果より、この接合方法が、ペースト状銅粒子組成物中の銅粒子を強固に焼結し、銅基板と銅チップを酸化することなく強固に接合するのに有用なことがわかった。 A paste-like copper particle composition was prepared under the same conditions as in Example 6 except that the flaky copper particles were used instead of the copper particles used in Example 6.
As a reducing gas, a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume is used to produce a specimen for hardness measurement and a specimen for bonding strength measurement in a gas flow furnace. did. These test specimens were measured and evaluated for hardness, bonding strength, and oxidation of the copper substrate and the copper chip, and the results are shown in Table 1. From the above results, it has been found that this joining method is useful for strongly sintering the copper particles in the paste-like copper particle composition and strongly joining the copper substrate and the copper chip without being oxidized.
［実施例８］
厚さが１.２ｍｍのアルミナ板上に形成された銅製配線回路（幅１ｍｍ、長さ５０ｍｍ、厚さ３０μｍ）の両端部に、縦１ｍｍ、横１ｍｍ、厚さ１００μｍの開口部を有するメタルマスクを用いて実施例１のペースト状銀粒子組成物をドット状に印刷塗布した。
このアルミナ板を室温のガス流通炉に入れ、還元性ガスとして、水素ガス濃度が１０体積％であり窒素ガス濃度が９０体積％である混合ガスを用い、ガス置換後、ガスを流量１リットル／分で流しながら室温から昇温速度１℃／秒で３００℃まで昇温し、３００℃で１時間保持後、室温まで冷却してペースト状銀粒子組成物中の銀粒子を焼結し、電気回路接続用バンプを製造した。
この電気回路の両端部に形成した電気回路接続用バンプ間の電気抵抗を測定したところ、０.０５Ω未満であり、実用上十分な導電性を有していた。 [Example 8]
Metal mask having openings of 1 mm in length, 1 mm in width, and 100 μm in thickness at both ends of a copper wiring circuit (width 1 mm, length 50 mm, thickness 30 μm) formed on an alumina plate having a thickness of 1.2 mm The paste-like silver particle composition of Example 1 was printed and applied in dots.
This alumina plate was placed in a gas flow furnace at room temperature, and as a reducing gas, a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume was used. The temperature was raised from room temperature to 300 ° C. at a heating rate of 1 ° C./second while flowing in minutes, held at 300 ° C. for 1 hour, then cooled to room temperature to sinter the silver particles in the paste-like silver particle composition, A bump for circuit connection was manufactured.
When the electric resistance between the electric circuit connecting bumps formed at both ends of the electric circuit was measured, it was less than 0.05Ω, and the electric conductivity was sufficiently practical.
［実施例９］
厚さが１.２ｍｍのアルミナ板上に形成された銅製配線回路（幅１ｍｍ、長さ５０ｍｍ、厚さ３０μｍ）の両端部に、縦１ｍｍ、横１ｍｍ、厚さ１００μｍの開口部を有するメタルマスクを用いて実施例６のペースト状銅粒子組成物をドット状に印刷塗布した。
このアルミナ板を室温のガス流通炉に入れ、還元性ガスとして、水素ガス濃度が１０体積％であり窒素ガス濃度が９０体積％である混合ガスを用い、ガス置換後、ガスを流量１リットル／分で流しながら室温から昇温速度１℃／秒で３００℃まで昇温し、３００℃で１時間保持後、室温まで冷却してペースト状銅粒子組成物中の銅粒子を焼結し、電気回路接続用バンプを製造した。
この電気回路の両端部に形成した電気回路接続用バンプ間の電気抵抗を測定したところ、０.１Ω未満であり、実用上十分な導電性を有していた。 [Example 9]
Metal mask having openings of 1 mm in length, 1 mm in width, and 100 μm in thickness at both ends of a copper wiring circuit (width 1 mm, length 50 mm, thickness 30 μm) formed on an alumina plate having a thickness of 1.2 mm The paste-like copper particle composition of Example 6 was printed and applied in dots.
This alumina plate was placed in a gas flow furnace at room temperature, and as a reducing gas, a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume was used. The temperature is raised from room temperature to 300 ° C. at a heating rate of 1 ° C./second while flowing in minutes, held at 300 ° C. for 1 hour, then cooled to room temperature to sinter the copper particles in the paste-like copper particle composition, A bump for circuit connection was manufactured.
When the electric resistance between the electric circuit connecting bumps formed at both ends of the electric circuit was measured, it was less than 0.1Ω, and the electric conductivity was sufficiently practical.
[比較例１]
実施例１において、水素ガス濃度が１０体積％であり窒素ガス濃度が９０体積％である還元性ガスの代わりに、窒素ガス（窒素ガス濃度が９９.９９体積％以上である）を用いた以外は実施例１と同様の条件で、硬さ測定用の試験体および接合強度測定用の試験体を作製し、硬さ、接合強度、および、銅基板の酸化の測定、評価をし、結果を表２にまとめて示した。 [Comparative Example 1]
In Example 1, instead of the reducing gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume, nitrogen gas (the nitrogen gas concentration is 99.99% by volume or more) was used. Are the same conditions as in Example 1 to prepare a test specimen for hardness measurement and a test specimen for bond strength measurement, and measure and evaluate the hardness, the bond strength, and the oxidation of the copper substrate. Table 2 summarizes the results.
[比較例２]
実施例１において、水素ガス濃度が１０体積％であり窒素ガス濃度が９０体積％である還元性ガスの代わりに、圧縮空気（窒素ガス濃度が７８.０体積％である）を用いた以外は実施例１と同様の条件で、硬さ測定用の試験体および接合強度測定用の試験体を作製し、硬さ、接合強度、および、銅基板の酸化の測定、評価をし、結果を表２にまとめて示した。 [Comparative Example 2]
In Example 1, instead of the reducing gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume, compressed air (nitrogen gas concentration is 78.0% by volume) was used. Under the same conditions as in Example 1, a specimen for hardness measurement and a specimen for joint strength measurement were prepared, and the hardness, the joint strength, and the oxidation of the copper substrate were measured and evaluated. 2 collectively.
[比較例３]
実施例１において、水素ガス濃度が１０体積％であり窒素ガス濃度が９０体積％である還元性ガスの代わりに、窒素ガス濃度が９８体積％であり酸素ガス濃度が２体積％である調製ガスを用いた以外は実施例１と同様の条件で、硬さ測定用の試験体および接合強度測定用の試験体を作製し、硬さ、接合強度、および、銅基板の酸化の測定、評価をし、結果を表２にまとめて示した。 [Comparative Example 3]
In Example 1, instead of the reducing gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume, a prepared gas having a nitrogen gas concentration of 98% by volume and an oxygen gas concentration of 2% by volume. A test body for hardness measurement and a test body for bonding strength measurement were prepared under the same conditions as in Example 1 except that the hardness, bonding strength, and oxidation of the copper substrate were measured and evaluated. The results are summarized in Table 2.
[比較例４]
ボールミルに、市販の還元法で製造された銀粒子（形状：粒状、１次粒子の平均粒径：１.０μｍ、撥水性有機物による被覆なし）を投入し、ベンゾトリアゾール（和光純薬工業株式会社製、試薬１級）のイソプロピルアルコール溶液を添加して稼働し、乾燥することにより、表面がベンゾトリアゾールで被覆されたフレーク状銀粒子（１次粒子の平均粒径：４.２μｍ、親水性有機物であるベンゾトリアゾール量：０.５重量％）を調製した。
実施例１で使用したステアリン酸被覆銀粒子の代わりに、上記ベンゾトリアゾール被覆銀粒子を用いたほかは、実施例１と同様の条件でペースト状銀粒子組成物を調製した。 [Comparative Example 4]
Silver particles (shape: granular, average primary particle size: 1.0 μm, uncoated with water repellent organic matter) produced by a commercially available reduction method were introduced into a ball mill, and benzotriazole (Wako Pure Chemical Industries, Ltd.) The product is operated by adding an isopropyl alcohol solution (made by Reagent Grade 1), and dried to obtain flaky silver particles whose surface is coated with benzotriazole (average particle size of primary particles: 4.2 μm, hydrophilic organic substance) Benzotriazole amount: 0.5% by weight) was prepared.
A pasty silver particle composition was prepared under the same conditions as in Example 1 except that the benzotriazole-coated silver particles were used in place of the stearic acid-coated silver particles used in Example 1.
還元性ガスとして、水素ガス濃度が１０体積％であり窒素ガス濃度が９０体積％である混合ガスを用い、ガス流通炉内で硬さ測定用の試験体および接合強度測定用の試験体を作製した。これらの試験体について、硬さ、接合強度、および、銅基板の酸化の測定、評価をし、結果を表２にまとめて示した。 As a reducing gas, a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume is used to produce a specimen for hardness measurement and a specimen for bonding strength measurement in a gas flow furnace. did. These test specimens were measured and evaluated for hardness, bonding strength, and oxidation of the copper substrate, and the results are summarized in Table 2.
[比較例５]
実施例１において、表面がステアリン酸で被覆された銀粒子の代わりに、表面が撥水性有機物で被覆されていない銀粒子（形状：粒状、１次粒子の平均粒径：１.１μｍ）を使用した以外は同様の条件でペースト状銀粒子組成物を調製した。
還元性ガスとして、水素ガス濃度が１０体積％であり窒素ガス濃度が９０体積％である混合ガスを用い、ガス流通炉で硬さ測定用の試験体および接合強度測定用の試験体を作製した。これらの試験体について、硬さ、接合強度、および、銅基板の酸化の測定、評価をし、結果を表２にまとめて示した。 [Comparative Example 5]
In Example 1, instead of silver particles whose surface is coated with stearic acid, silver particles whose surface is not coated with a water-repellent organic material (shape: granular, average particle size of primary particles: 1.1 μm) are used. Except that, a paste-like silver particle composition was prepared under the same conditions.
As a reducing gas, a mixed gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume was used to produce a specimen for hardness measurement and a specimen for bonding strength measurement in a gas flow furnace. . These test specimens were measured and evaluated for hardness, bonding strength, and oxidation of the copper substrate, and the results are summarized in Table 2.
[比較例６]
実施例６において、水素ガス濃度が１０体積％であり窒素ガス濃度が９０体積％である還元性ガスの代わりに、圧縮空気（窒素ガス濃度が７８.０体積％である）を用いた以外は実施例６と同様の条件で、硬さ測定用の試験体および接合強度測定用の試験体を作製し、硬さ、接合強度、および、銅基板の酸化の測定、評価をし、結果を表２にまとめて示した。 [Comparative Example 6]
In Example 6, instead of the reducing gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume, compressed air (nitrogen gas concentration is 78.0% by volume) was used. Under the same conditions as in Example 6, a specimen for hardness measurement and a specimen for joint strength measurement were prepared, and the hardness, the joint strength, and the oxidation of the copper substrate were measured and evaluated. 2 collectively.
[比較例７]
実施例６において、水素ガス濃度が１０体積％であり窒素ガス濃度が９０体積％である還元性ガスの代わりに、窒素ガス（窒素ガス濃度が９９.９９体積％以上である）を用いた以外は実施例６と同様の条件で、硬さ測定用の試験体および接合強度測定用の試験体を作製し、硬さ、接合強度、および、銅基板の酸化の測定、評価をし、結果を表２にまとめて示した。 [Comparative Example 7]
In Example 6, instead of the reducing gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume, nitrogen gas (the nitrogen gas concentration is 99.99% by volume or more) was used. Are the same as in Example 6 to prepare a test specimen for hardness measurement and a test specimen for bond strength measurement, and measure and evaluate the hardness, the bond strength, and the oxidation of the copper substrate. Table 2 summarizes the results.
[比較例８]
実施例７において、水素ガス濃度が１０体積％であり窒素ガス濃度が９０体積％である還元性ガスの代わりに、圧縮空気（窒素ガス濃度が７８.０体積％である）を用いた以外は実施例７と同様の条件で、硬さ測定用の試験体および接合強度測定用の試験体を作製し、硬さ、接合強度、および、銅基板の酸化の測定、評価をし、結果を表２にまとめて示した。 [Comparative Example 8]
In Example 7, instead of the reducing gas having a hydrogen gas concentration of 10% by volume and a nitrogen gas concentration of 90% by volume, compressed air (nitrogen gas concentration is 78.0% by volume) was used. Under the same conditions as in Example 7, a specimen for hardness measurement and a specimen for joint strength measurement were prepared, and the hardness, the joint strength, and the oxidation of the copper substrate were measured and evaluated. 2 collectively.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
本発明の金属製部材の接合方法は、プラズマ処理しなくても、酸化して腐食や変色がしやすい金属製部材同士を、酸化することなく強固に接合させることができるので、コンデンサ、抵抗、ダイオード、メモリ、演算素子（ＣＰＵ）等のチップ部品の基板への接合、放熱用部材の接合などに有用である。
本発明の金属製部材接合体は、電子部品、電子装置、電気部品、電気装置などとして有用である。
本発明の電気回路接続用バンプの製造方法は、半導体素子または基板上に金属製バンプを効率よく製造するのに有用である。 Since the metal member joining method of the present invention can strongly join metal members that are easily oxidized and corroded or discolored without being plasma-treated without being oxidized, capacitors, resistors, This is useful for bonding chip components such as diodes, memories, and arithmetic elements (CPUs) to substrates, and for radiating heat dissipation members.
The metal member assembly of the present invention is useful as an electronic component, an electronic device, an electrical component, an electrical device, or the like.
The method for manufacturing a bump for connecting an electric circuit of the present invention is useful for efficiently manufacturing a metal bump on a semiconductor element or a substrate.

Claims (15)

  1. (A)平均粒径が０.１μｍより大きく５０μｍ以下であり非アミン系撥水性有機物で被覆された加熱焼結性金属粒子と、(B)揮発性分散媒とからなるペースト状金属粒子組成物を複数の金属製部材間に介在させ、還元性ガス中で７０℃以上４００℃以下での加熱により、該揮発性分散媒を揮散させ該金属粒子同士を焼結して複数の金属製部材同士を接合させることを特徴とする、金属製部材の接合方法。 A paste-like metal particle composition comprising (A) a heat-sinterable metal particle having an average particle size greater than 0.1 μm and not more than 50 μm and coated with a non-amine water-repellent organic material, and (B) a volatile dispersion medium. Is interposed between a plurality of metal members, and the volatile dispersion medium is volatilized by heating at 70 ° C. to 400 ° C. in a reducing gas to sinter the metal particles to each other. A method for joining metal members, characterized in that:
  2. 還元性ガスが水素ガスまたは水素ガス含有ガスであることを特徴とする、請求項１に記載の接合方法。 The joining method according to claim 1, wherein the reducing gas is hydrogen gas or a hydrogen gas-containing gas.
  3. 水素ガス含有ガスが水素ガスと不活性ガスの混合物であり、水素ガスの濃度が１～４０体積％であることを特徴とする、請求項２に記載の接合方法。 The joining method according to claim 2, wherein the hydrogen gas-containing gas is a mixture of hydrogen gas and inert gas, and the concentration of hydrogen gas is 1 to 40% by volume.
  4. 非アミン系撥水性有機物が高・中級脂肪酸またはその誘導体であることを特徴とする、請求項１に記載の接合方法。 The joining method according to claim 1, wherein the non-amine water-repellent organic substance is a high / intermediate fatty acid or a derivative thereof.
  5. 高・中級脂肪酸は炭素原子数が６～２４であり、その誘導体が高・中級脂肪酸金属塩（アルカリ金属塩を除く）、高・中級脂肪酸アミドまたは高・中級脂肪酸エステルであることを特徴とする、請求項４に記載の接合方法。 High / intermediate fatty acids have 6 to 24 carbon atoms, and their derivatives are high / intermediate fatty acid metal salts (excluding alkali metal salts), high / intermediate fatty acid amides or high / intermediate fatty acid esters. The joining method according to claim 4.
  6. 加熱焼結性金属粒子の金属が銀、銀合金、銅または銅合金であり、かつ、金属製部材の金属が銅、銀、金、白金、パラジウム、または、これら各金属の合金であることを特徴とする、請求項１に記載の接合方法。 The metal of the heat-sinterable metal particles is silver, silver alloy, copper or copper alloy, and the metal of the metal member is copper, silver, gold, platinum, palladium, or an alloy of each of these metals The joining method according to claim 1, wherein the joining method is characterized.
  7. 非アミン系撥水性有機物が高・中級脂肪酸またはその誘導体であり、加熱焼結性金属粒子の金属が銀、銀合金、銅または銅合金であり、かつ、金属製部材の金属が銅、銀、金、白金、パラジウム、または、これら各金属の合金であることを特徴とする、請求項１に記載の接合方法。 The non-amine water-repellent organic substance is a high / intermediate fatty acid or derivative thereof, the metal of the heat-sinterable metal particles is silver, silver alloy, copper or copper alloy, and the metal of the metal member is copper, silver, The joining method according to claim 1, wherein the joining method is gold, platinum, palladium, or an alloy of these metals.
  8. 還元性ガスが水素ガスまたは水素ガス含有ガスであり、非アミン系撥水性有機物が高・中級脂肪酸またはその誘導体であり、加熱焼結性金属粒子の金属が銀、銀合金、銅または銅合金であり、かつ、金属製部材の金属が銅、銀、金、白金、パラジウム、または、これら各金属の合金であることを特徴とする、請求項１に記載の接合方法。 The reducing gas is hydrogen gas or a gas containing hydrogen gas, the non-amine water-repellent organic substance is a high / intermediate fatty acid or derivative thereof, and the metal of the heat-sinterable metal particles is silver, silver alloy, copper or copper alloy. The joining method according to claim 1, wherein the metal of the metal member is copper, silver, gold, platinum, palladium, or an alloy of these metals.
  9. 水素ガス含有ガスが水素ガスと不活性ガスの混合物であり、水素ガスの濃度が１～４０体積％であり、高・中級脂肪酸は炭素原子数が６～２４であり、その誘導体が高・中級脂肪酸金属塩（アルカリ金属塩を除く）、高・中級脂肪酸アミドまたは高・中級脂肪酸エステルであることを特徴とする、請求項８に記載の接合方法。 The hydrogen gas-containing gas is a mixture of hydrogen gas and inert gas, the concentration of hydrogen gas is 1 to 40% by volume, high and intermediate fatty acids have 6 to 24 carbon atoms, and their derivatives are high and intermediate The joining method according to claim 8, wherein the joining method is a fatty acid metal salt (excluding an alkali metal salt), a high / intermediate fatty acid amide, or a high / intermediate fatty acid ester.
  10. 複数の金属製部材間で、平均粒径が０.１μｍより大きく５０μｍ以下であり非アミン系撥水性有機物で被覆された加熱焼結性金属粒子が、還元性ガス中で加熱焼結してなることを特徴とする、金属製部材接合体。 Heat-sinterable metal particles coated with a non-amine water-repellent organic substance and having an average particle size of more than 0.1 μm and not more than 50 μm between a plurality of metal members are heated and sintered in a reducing gas. A metal member assembly, characterized by that.
  11. 還元性ガスが水素ガスまたは水素ガス含有ガスであり、非アミン系撥水性有機物が高・中級脂肪酸またはその誘導体であり、加熱焼結性金属粒子の金属が銀、銀合金、銅または銅合金であり、かつ、金属製部材の金属が銅、銀、金、白金、パラジウム、または、これら各金属の合金であることを特徴とする、請求項１０に記載の金属製部材接合体。 The reducing gas is hydrogen gas or a gas containing hydrogen gas, the non-amine water-repellent organic substance is a high / intermediate fatty acid or derivative thereof, and the metal of the heat-sinterable metal particles is silver, silver alloy, copper or copper alloy. The metal member assembly according to claim 10, wherein the metal of the metal member is copper, silver, gold, platinum, palladium, or an alloy of these metals.
  12. 水素ガス含有ガスが水素ガスと不活性ガスの混合物であり、水素ガスの濃度が１～４０体積％であり、高・中級脂肪酸は炭素原子数が６～２４であり、その誘導体が高・中級脂肪酸金属塩（アルカリ金属塩を除く）、高・中級脂肪酸アミドまたは高・中級脂肪酸エステルであることを特徴とする、請求項１１に記載の金属製部材接合体。 The hydrogen gas-containing gas is a mixture of hydrogen gas and inert gas, the concentration of hydrogen gas is 1 to 40% by volume, high and intermediate fatty acids have 6 to 24 carbon atoms, and their derivatives are high and intermediate The metal member joined body according to claim 11, which is a fatty acid metal salt (excluding an alkali metal salt), a high / intermediate fatty acid amide, or a high / intermediate fatty acid ester.
  13. (A)平均粒径が０.１μｍより大きく５０μｍ以下であり非アミン系撥水性有機物で被覆された加熱焼結性金属粒子と、(B)揮発性分散媒とからなるペースト状金属粒子組成物を半導体素子上の電気回路接続用パッド部または基板上の電気回路接続用電極部にドット状に塗布し、還元性ガス中で７０℃以上４００℃以下での加熱により、該揮発性分散媒を揮散させ該金属粒子同士を焼結して、半導体素子上または基板上に金属粒子製バンプを形成することを特徴とする、電気回路接続用バンプの製造方法。 A paste-like metal particle composition comprising (A) a heat-sinterable metal particle having an average particle size greater than 0.1 μm and not more than 50 μm and coated with a non-amine water-repellent organic material, and (B) a volatile dispersion medium. Is applied in the form of dots to an electric circuit connecting pad on a semiconductor element or an electric circuit connecting electrode on a substrate, and the volatile dispersion medium is removed by heating at 70 ° C. to 400 ° C. in a reducing gas. A method for producing a bump for connecting an electric circuit, comprising volatilizing and sintering the metal particles to form a bump made of metal particles on a semiconductor element or a substrate.
  14. 還元性ガスが水素ガスまたは水素ガス含有ガスであり、非アミン系撥水性有機物が高・中級脂肪酸またはその誘導体であり、加熱焼結性金属粒子の金属が銀、銀合金、銅または銅合金であり、かつ、電気回路接続用パッド部または基板上の電気回路接続用電極部の金属が銅、銀、金、白金、パラジウム、または、これら各金属の合金であることを特徴とする、請求項１３に記載の電気回路接続用バンプの製造方法。 The reducing gas is hydrogen gas or a gas containing hydrogen gas, the non-amine water-repellent organic substance is a high / intermediate fatty acid or derivative thereof, and the metal of the heat-sinterable metal particles is silver, silver alloy, copper or copper alloy. And the metal of the electric circuit connecting pad section or the electric circuit connecting electrode section on the substrate is copper, silver, gold, platinum, palladium, or an alloy of these metals. 14. A method for manufacturing an electric circuit connecting bump according to 13.
  15. 水素ガス含有ガスが水素ガスと不活性ガスの混合物であり、水素ガスの濃度が１～４０体積％であり、高・中級脂肪酸は炭素原子数が６～２４であり、その誘導体が高・中級脂肪酸金属塩（アルカリ金属塩を除く）、高・中級脂肪酸アミドまたは高・中級脂肪酸エステルであることを特徴とする、請求項１４に記載の電気回路接続用バンプの製造方法。 The hydrogen gas-containing gas is a mixture of hydrogen gas and inert gas, the concentration of hydrogen gas is 1 to 40% by volume, high and intermediate fatty acids have 6 to 24 carbon atoms, and their derivatives are high and intermediate 15. The method for producing an electric circuit connecting bump according to claim 14, wherein the method is a fatty acid metal salt (excluding an alkali metal salt), a high / intermediate fatty acid amide, or a high / intermediate fatty acid ester.
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