WO2010098357A1 - Charge métallique, brasage sans plomb de connexion basse température, et structure de connexion - Google Patents

Charge métallique, brasage sans plomb de connexion basse température, et structure de connexion Download PDF

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Publication number
WO2010098357A1
WO2010098357A1 PCT/JP2010/052880 JP2010052880W WO2010098357A1 WO 2010098357 A1 WO2010098357 A1 WO 2010098357A1 JP 2010052880 W JP2010052880 W JP 2010052880W WO 2010098357 A1 WO2010098357 A1 WO 2010098357A1
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WIPO (PCT)
Prior art keywords
metal particles
metal
mass
particles
solder
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PCT/JP2010/052880
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English (en)
Japanese (ja)
Inventor
朋紀 木山
軌人 田中
Original Assignee
旭化成イーマテリアルズ株式会社
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Application filed by 旭化成イーマテリアルズ株式会社 filed Critical 旭化成イーマテリアルズ株式会社
Priority to JP2011501623A priority Critical patent/JP5643972B2/ja
Priority to KR1020117017424A priority patent/KR101230195B1/ko
Priority to CN201080007347.9A priority patent/CN102317031B/zh
Publication of WO2010098357A1 publication Critical patent/WO2010098357A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/264—Bi as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/302—Cu as the principal constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C12/00—Alloys based on antimony or bismuth
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3457—Solder materials or compositions; Methods of application thereof
    • H05K3/3485—Applying solder paste, slurry or powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2101/00—Articles made by soldering, welding or cutting
    • B23K2101/36—Electric or electronic devices
    • B23K2101/40—Semiconductor devices
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0263—Details about a collection of particles
    • H05K2201/0272—Mixed conductive particles, i.e. using different conductive particles, e.g. differing in shape

Definitions

  • the present invention relates to a metal filler that can be used for connecting various electronic components and filling vias, etc., and a lead-free solder containing the metal filler, particularly a lead-free solder for low-temperature connection.
  • the present invention also relates to a connection structure obtained by using the lead-free solder, and a component mounting board having the connection structure and the substrate.
  • Sn-37Pb eutectic solder having a melting point of 183 ° C. has generally been used as a solder material used in reflow heat treatment. Further, as a high-temperature solder used inside an electronic component that requires high heat resistance, Sn-90Pb high-temperature solder having a solidus line of 270 ° C. and a liquidus line of 305 ° C. has been widely used.
  • the above-mentioned lead-free solder composed of Sn-3.0Ag-0.5Cu having a melting point of about 220 ° C. has a higher melting point of the alloy than Sn-37Pb eutectic solder, and therefore the reflow heat treatment conditions become higher.
  • the lowering of the reflow heat treatment temperature is expected from the fact that it is possible to suppress the thermal damage of the electric / electronic equipment and the substrate material, and the range of selection of the usable substrate material is expanded.
  • Sn-58Bi eutectic solder melting point 138 ° C.
  • In melting point 157 ° C.
  • Sn-52In alloy solder melting point 118 ° C.
  • all of these solder materials have a low melting point, and have a problem that they are remelted when the temperature again becomes higher than the melting point after soldering.
  • the present inventors have proposed a highly heat-resistant solder material that can be melt-bonded under reflow heat treatment conditions of lead-free solder, such as a peak temperature of 246 ° C., and does not melt under the same heat-treatment conditions after bonding (Patent Document 3).
  • the metal particles contained in the solder material are a mixture of first metal particles and second metal particles having a lower melting point than the first metal particles.
  • Sn is used as the second metal particles.
  • bonding can be performed at a lower temperature, and after bonding, re-melting is not performed under reflow heat treatment conditions of lead-free solder. Material is desired.
  • solder material that can be melt-bonded at a peak temperature of 149 ° C. or higher and that has heat resistance under a heat treatment condition of 260 ° C. after the bonding (Patent Document 4).
  • the conductive filler contained in the solder material is a mixture of first metal particles and second metal particles having a melting point higher than that of the first metal particles.
  • solder paste using a mixture of Cu powder and Sn—Bi-based powder alloy has been proposed as a solder paste that includes a plurality of types of metal particles and can be bonded at a low temperature. (See Patent Document 5).
  • JP 2001-334386 A Japanese Patent Laid-Open No. 11-239866 International Publication No. 2006/109573 Pamphlet JP 2008-183582 A JP 2008-200788 A
  • the present invention has been made in view of the above problems, and can be melt-bonded at a temperature lower than the reflow heat treatment conditions of Sn-37Pb eutectic solder (for example, a peak temperature of 160 ° C.), and good bonding at room temperature after bonding. It aims at providing the metal filler which can give intensity
  • Another object of the present invention is to provide a lead-free solder containing the metal filler, a connection structure obtained by using the lead-free solder, and a component mounting board having the connection structure and the substrate.
  • a metal filler comprising a mixture of first metal particles and second metal particles
  • the first metal particles are Cu alloy particles containing Cu as a main component which is an element present in the highest mass ratio, and further containing In and Sn
  • the second metal particles are Bi alloy particles composed of Bi 40 to 70% by mass, and 30 to 60% by mass of one or more metals selected from the group consisting of Ag, Cu, In and Sn, and A metal filler, wherein the amount of the second metal particles is 40 to 300 parts by mass with respect to 100 parts by mass of the first metal particles.
  • the first metal particles are composed of Ag 5 to 15% by mass, Bi 2 to 8% by mass, Cu 49 to 81% by mass, In 2 to 8% by mass, and Sn 10 to 20% by mass, In the differential scanning calorimetry (DSC), the first metal particles have at least one exothermic peak observed in the range of 230 to 300 ° C. and at least one endothermic peak observed in the range of 480 to 530 ° C.
  • the metal filler of the present invention and the lead-free solder containing the metal filler can be melt-bonded under conditions lower than the reflow heat treatment conditions of, for example, Sn-37Pb eutectic solder (for example, a peak temperature of 160 ° C. or higher).
  • the solder joint does not remelt even after multiple heat treatments. Therefore, according to the present invention, an effect of preventing a short circuit due to remelting of solder that occurs between component electrodes and the like can be obtained.
  • the metal filler of this invention and the lead-free solder containing this metal filler can give the favorable joint strength at room temperature after joining.
  • the metal filler of the present invention is a metal filler composed of a mixture of first metal particles and second metal particles, and the first metal particles are Cu (copper) as a main component which is an element present in the highest mass ratio. ) And further containing In (indium) and Sn (tin), the second metal particles are Bi (bismuth) 40 to 70 mass%, and Ag (silver), Cu (Bi) alloy particles composed of 30 to 60% by mass of one or more kinds of metals selected from the group consisting of (copper), In (indium) and Sn (tin), and the second metal with respect to 100 parts by mass of the first metal particles. The amount of metal particles is 40 to 300 parts by mass.
  • the melting point of the first metal particles is set higher than the melting point of the second metal particles by the combination of the first metal particles and the second metal particles having the above composition.
  • the second metal particles having a melting point lower than that of the first metal particles are melted, and an alloying reaction due to thermal diffusion occurs between the first metal particles and the melted second metal particles, A stable alloy phase having a melting point higher than that of the second metal particles is formed.
  • the first metal particles do not melt at the reflow heat treatment temperature when using the lead-free solder according to the present invention.
  • the lead-free solder containing the metal filler of the present invention can be melt-bonded at a low temperature condition (typically, a temperature lower than the reflow heat treatment condition of Sn-37Pb eutectic solder) and melt-bonded. Later, it has the effect of not being remelted by heat treatment.
  • a low temperature condition typically, a temperature lower than the reflow heat treatment condition of Sn-37Pb eutectic solder
  • the possibility of low-temperature melt bonding is advantageous in that it can be used in an energy saving process and a low carbon dioxide emission process, and heat damage of applied electric / electronic devices and substrate materials can be suppressed.
  • the combination of the first metal particles and the second metal particles having the above composition can avoid the problem of aggregation due to moisture absorption that occurs when, for example, Cu powder is used.
  • the first metal particles have a composition containing Cu as a main component and the second metal particles contain a large amount of Bi.
  • a metal filler that can be melt-bonded at a low temperature, has a good bonding strength at room temperature after bonding, and reduces the amount of expensive metals such as In and Ag.
  • the first metal particles have Cu as a main component. That is, the mass ratio of Cu is the largest among the elements constituting the first metal particles.
  • the first metal particles further contain In and Sn in addition to Cu. Thereby, the first metal particles can form a metastable alloy phase.
  • the formation of the metastable alloy phase contributes to the promotion of alloying between the first metal particles and the second metal particles, and therefore contributes to the provision of a good bonding strength at the time of fusion bonding at a low temperature.
  • the first metal particles further contain one or more metals selected from Ag and Bi, in addition to Cu, In and Sn, from the viewpoint of favorably realizing alloying by thermal diffusion with the second metal particles. Is preferred.
  • the first metal particles comprise Ag 5 to 15% by mass, Bi 2 to 8% by mass, Cu 49 to 81% by mass, In 2 to 8% by mass, and Sn 10 to 20% by mass. In this case, inevitable impurities may be included.
  • the first metal particles have at least one exothermic peak observed in the range of 230 to 300 ° C. and at least 1 observed in the range of 480 to 530 ° C. in differential scanning calorimetry (DSC). With two endothermic peaks. The exothermic peak observed within the range of 230 to 300 ° C. indicates that the first metal particles form a metastable alloy phase, and the endothermic peak observed within the range of 480 to 530 ° C. The melting point of the metal particles is shown. In addition, melting
  • the first metal particles are composed of Ag 5 to 15% by mass, Bi 2 to 8% by mass, Cu 49 to 81% by mass, In 2 to 8% by mass, and Sn 10 to 20% by mass, and the first metal The particles have at least one exothermic peak observed in the range of 230-300 ° C. and at least one endothermic peak observed in the range of 480-530 ° C. in differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the average particle diameter of the first metal particles is preferably in the range of 2 to 30 ⁇ m.
  • the average particle diameter of the first metal particles is 2 ⁇ m or more, the specific surface area of the particles becomes small. Therefore, when forming a solder paste from the metal filler of the present invention using, for example, a flux described later, there is an advantage that the contact area between the first metal particles and the flux is reduced and the life of the solder paste is increased. .
  • outgas generated by the reduction reaction of the metal filler by the flux that is, removal of the oxide film of the metal filler particles
  • Voids generated inside the solder connection can be reduced.
  • the average particle diameter of the first metal particles is preferably 30 ⁇ m or less from the viewpoint of the adhesive strength of the solder paste. If the particle size becomes too large, the gaps between the particles become large, so the adhesive strength of the solder paste is likely to be impaired, and the component is likely to come off from the mounting of the component to be soldered to the end of the reflow heat treatment. .
  • the average particle diameter of the first metal particles is more preferably in the range of 5 to 25 ⁇ m.
  • the average particle diameter in this specification is a value measured by a laser diffraction particle size distribution measuring apparatus.
  • the second metal particles are composed of Bi 40 to 70% by mass and 30 to 60% by mass of one or more metals selected from Ag, Cu, In and Sn. In this case, inevitable impurities may be contained. With the above composition, the second metal particles can be melted in the reflow heat treatment, and the alloying by thermal diffusion is favorably realized between the first metal particles and the melted second metal particles.
  • the content of Bi in the second metal particles is 40% by mass or more and 70% by mass or less from the viewpoint of enabling fusion bonding at low temperature and obtaining good bonding strength at room temperature after bonding.
  • the content is preferably 50 to 60% by mass.
  • the content of one or more metals selected from Ag, Cu, In and Sn in the second metal particles is 30% by mass from the viewpoint of favorably realizing alloying of the first metal particles and the second metal particles. From the viewpoint of allowing a sufficient amount of Bi to be contained in the second metal particles and enabling fusion bonding at a low temperature, it is 60% by mass or less. The content is preferably 40 to 50% by mass.
  • the second metal particles contain Sn.
  • Sn sulfur
  • the content of Sn in the second metal particles is preferably 40 to 50% by mass.
  • the second metal particles contain one or more metals selected from Ag, Cu, and In, it is possible to improve ductility, lower melting point, mechanical strength, and the like.
  • the second metal particles are more preferably Sn—Bi alloy particles, and more preferably a eutectic composition (typically Sn that hardly causes solidification defects and segregation).
  • Sn—Bi alloy particles contain only Sn and Bi as constituent elements (however, they may contain inevitable impurities), but they have improved ductility, lower melting point, mechanical strength, etc.
  • a trace amount of one or more metals selected from Ag, Cu and In may be added.
  • the average particle diameter of the second metal particles is preferably in the range of 5 to 40 ⁇ m from the same reason as the average particle diameter of the first metal particles, that is, from the viewpoint of the reactivity with the flux and the adhesive strength of the paste.
  • the average particle diameter of the first metal particles is more preferably in the range of 5 to 25 ⁇ m.
  • the metal filler of the present invention comprises a mixture of first metal particles and second metal particles.
  • the amount of the second metal particles with respect to 100 parts by mass of the first metal particles (hereinafter also referred to as “mixing ratio of the second metal particles”) is in the range of 40 to 300 parts by mass.
  • the mixing ratio of the second metal particles is 40 parts by mass or more, the presence of the component that melts during the reflow heat treatment in the metal filler is large, so that fusion bonding at a low temperature can be carried out satisfactorily. Good physical strength is imparted after being joined.
  • the mixing ratio of the second metal particles is 100 parts by mass or more, better physical strength can be obtained.
  • the mixing ratio of the second metal particles exceeds 300 parts by mass, the existence ratio of the high melting point stable alloy phase formed by the reaction of the molten second metal particles with the first metal particles is small. Heat resistance cannot be obtained.
  • the mixing ratio of the second metal particles is preferably in the range of 100 to 300 parts by mass.
  • the particle size distribution of the first metal particles and the second metal particles can be determined according to the solder paste application. For example, in screen printing applications, emphasis is placed on plate spillability, and it is preferable to make the particle size distribution broad. In dispensing applications and via filling applications, emphasis is placed on discharge fluidity and hole filling properties, and the particle size distribution is sharp. It is preferable to do this.
  • the average particle diameters of the first metal particles and the second metal particles are preferably in the range of 2 to 30 ⁇ m and 5 to 40 ⁇ m, respectively, from the viewpoints of reactivity with the flux and paste properties.
  • the average particle diameters of the first metal particles and the second metal particles are both in the range of 5 to 25 ⁇ m.
  • the metal filler of the present invention can form a paste-like lead-free solder, for example, by being combined with a flux. When component mounting is performed using this solder paste, a thin flux layer may be formed on the surface of the solder joint, particularly the fillet portion, formed by reflow heat treatment.
  • the metal particles are likely to be entrained in a state where the fine particles of the metal filler are suspended in the flux layer (that is, the metal particles are separated from each other), and the solder-joined parts are subsequently subjected to a flux cleaning process.
  • the metal filler particles flow out into the cleaning liquid and adhere to the parts.
  • the average particle diameter of the first metal particles and the second metal particles is 5 ⁇ m or more, the fine particles of the metal filler are less likely to be entrained in the flux layer during component mounting, and the generation of floating particles in the flux layer can be suppressed. The number of particles flowing out can be reduced.
  • the average particle diameters of the first metal particles and the second metal particles are both 25 ⁇ m or less, the adhesive strength of the solder paste is hardly damaged.
  • the melting point of the second metal particles is preferably in the range of 80 to 160 ° C, more preferably in the range of 100 to 150 ° C.
  • the second metal particles melt at the reflow heat treatment temperature when using the lead-free solder according to the present invention.
  • the elemental composition of the first metal particles and the second metal particles defined in this specification can be confirmed by, for example, inductively coupled plasma (ICP) emission analysis.
  • ICP inductively coupled plasma
  • the elemental composition of the particle cross section can be analyzed by using SEM-EDX (characteristic X-ray analyzer).
  • a known method can be adopted as a method for producing fine powder, but a rapid solidification method is preferred.
  • the method for producing fine powder by the rapid solidification method include a water spray method, a gas spray method, and a centrifugal spray method.
  • the gas spraying method and the centrifugal spraying method are more preferable because the oxygen content of the particles can be suppressed.
  • an inert gas such as nitrogen gas, argon gas or helium gas can be usually used.
  • helium gas having a low specific gravity in that the linear velocity during gas spraying can be increased and the cooling rate can be increased.
  • the cooling rate is preferably in the range of 500 to 5000 ° C./second.
  • the material is preferably sialon, and the disk rotation speed is preferably in the range of 60,000 to 120,000 rpm.
  • the present invention also provides a lead-free solder containing the metal filler of the present invention described above.
  • lead-free means that the lead content is 0.1% by mass or less in accordance with EU environmental regulations.
  • the lead-free solder of the present invention is preferably a solder paste containing a metal filler component and a flux component.
  • the lead-free solder of the present invention more typically comprises a metal filler component and a flux component.
  • the metal filler component may be composed of the metal filler of the present invention described above, or may contain a small amount of other metal fillers as long as the effects of the present invention are not impaired.
  • the content of the metal filler component in the solder paste is preferably in the range of 84 to 94% by mass out of 100% by mass of the solder paste from the viewpoint of paste characteristics.
  • a more preferable range of the content can be determined according to the paste application. For example, in screen printing applications, emphasis is placed on plate slippage, and the content is preferably in the range of 87 to 91% by mass, and more preferably in the range of 88 to 90% by mass. In dispensing applications, the content is preferably in the range of 85 to 89% by mass, and more preferably in the range of 86 to 88% by mass, with emphasis on discharge fluidity.
  • the flux component preferably contains rosin, a solvent, an activator, and a thixotropic agent.
  • the above flux components are suitable for the surface treatment of the metal filler. That is, by removing the oxide film of the metal filler component in the solder paste during reflow heat treatment and suppressing reoxidation, alloying by melting and thermal diffusion of the metal is promoted.
  • a known material can be used as the flux component.
  • the present invention includes a first electronic component, a second electronic component, and a solder joint that joins the first electronic component and the second electronic component, the solder joint being the book described above.
  • a connection structure formed by subjecting the inventive lead-free solder to reflow heat treatment.
  • the combination of the first electronic component and the second electronic component include a combination of a substrate electrode and a mounted component electrode.
  • a method for joining the first electronic component and the second electronic component for forming the connection structure of the present invention a method of joining a mounting component electrode after applying a solder paste to a substrate electrode and joining them by reflow heat treatment
  • a solder paste is applied to the mounting component electrode or the substrate electrode, bumps are formed by reflow heat treatment, and then the mounting component electrode and the substrate electrode are overlapped and joined again by reflow heat treatment.
  • the electrodes can be connected by solder bonding between the electrodes.
  • the reflow heat treatment temperature is preferably in the range of 100 to 200 ° C, more preferably in the range of 120 to 190 ° C.
  • the reflow heat treatment temperature is typically set below the melting point of the first metal particles and above the melting point of the second metal particles.
  • the second metal particles are melted when a thermal history equal to or higher than the melting point of the second metal particles is given. 1 Metal particle and mounting component electrode and substrate electrode are joined. At this time, the thermal diffusion reaction proceeds at an accelerated rate between the first metal particles and the second metal particles, and a new stable alloy phase having a melting point higher than the melting point of the second metal particles is formed.
  • a connection structure for connecting the particles and the mounted component electrodes and the substrate electrode is formed.
  • the melting point of this new stable alloy phase is higher than the reflow heat treatment temperature (for example, about 260 ° C.) of lead-free solder made of Sn-3.0Ag-0.5Cu. Does not melt. Therefore, according to the present invention, it is possible to prevent a short circuit occurring between the component electrodes due to remelting of the solder.
  • the present invention also provides a component mounting board having a board and the above-described connection structure of the present invention mounted on the board.
  • Example 1 (1) Production of first metal particles Cu 6.5 kg (purity 99 mass% or more), Sn 1.5 kg (purity 99 mass% or more), Ag 1.0 kg (purity 99 mass% or more), Bi 0.5 kg (purity 99 mass%) Above, and In 0.5 kg (purity 99 mass% or more) (that is, the target element composition is Cu: 65 mass%, Sn: 15 mass%, Ag: 10 mass%, Bi: 5 mass%, and In: 5 mass) %) was placed in a graphite crucible and heated and melted to 1400 ° C. with a high-frequency induction heating device in a helium atmosphere of 99% by volume or more.
  • this molten metal is introduced into the spray tank in the helium gas atmosphere from the tip of the crucible, and then helium gas (purity 99 volume% or more, oxygen concentration 0.1 volume) from a gas nozzle provided in the vicinity of the crucible tip.
  • helium gas purity 99 volume% or more, oxygen concentration 0.1 volume
  • the first metal particles were produced by atomizing by spraying (less than%, pressure 2.5 MPa).
  • the cooling rate at this time was 2600 ° C./second.
  • the first metal particles were classified using an airflow classifier (Nisshin Engineering: TC-15N) at a setting of 20 ⁇ m, and after collecting the large particles, they were classified again at a setting of 30 ⁇ m, and the small particles were collected.
  • the collected alloy particles were measured with a laser diffraction particle size distribution analyzer (HELOS & RODOS), the average particle size was 15.1 ⁇ m.
  • the first metal particles were measured with a differential scanning calorimeter (Shimadzu Corporation: DSC-50) under a nitrogen atmosphere at a temperature rising rate of 10 ° C./min in the range of 40 to 580 ° C.
  • first metal particles obtained here are hereinafter referred to as first metal particles A.
  • first metal particles obtained by atomization were classified at a setting of 10 ⁇ m, and after collecting the large particles, they were classified again at a setting of 20 ⁇ m, and the small particles were collected.
  • the collected alloy particles were measured with a laser diffraction particle size distribution analyzer (HELOS & RODOS), and the average particle size was 8.1 ⁇ m.
  • the obtained first metal particles are hereinafter referred to as first metal particles B.
  • first metal particles obtained by atomization were classified at a setting of 1.6 ⁇ m, the large particle side was collected, and then classified again at a setting of 10 ⁇ m, and the small particle side was collected.
  • the collected alloy particles were measured with a laser diffraction particle size distribution analyzer (HELOS & RODOS), the average particle size was 2.7 ⁇ m.
  • the obtained first metal particles are hereinafter referred to as first metal particles C.
  • first metal particles D The obtained first metal particles are hereinafter referred to as first metal particles D.
  • the second metal particles include a solder powder Bi-42Sn having a particle size of 25 ⁇ m to 45 ⁇ m manufactured by Yamaishi Metal Co., Ltd. (element composition is Bi: 58 mass%, Sn: 42 mass%) (Hereinafter referred to as second metal particles A) or solder powder Bi-42Sn with a particle size of 10 ⁇ m to 25 ⁇ m manufactured by Yamaishi Metal Co., Ltd. (element composition is Bi: 58 mass%, Sn: 42 mass%) ( Hereinafter, the second metal particles B are used).
  • the melting point measured by the differential scanning calorimeter (Shimadzu Corporation: DSC-50) under the same measurement conditions as described above was 138 ° C.
  • the average particle diameter was 35 micrometers and 20.4 micrometers, respectively.
  • solder paste Said 1st metal particle A and 2nd metal particle A were mixed by mass ratio 100: 300, and it was set as the metal filler component. Next, 89.5% by mass of the metal filler component and 10.5% by mass of the flux (A) were mixed, and the mixture was added to a solder softener (Malcom: SPS-1) and a defoaming kneader (Matsuo Sangyo: SNB-350). Solder paste was produced in sequence.
  • the solder paste is printed on a Cu substrate having a size of 25 mm ⁇ 25 mm and a thickness of 0.25 mm, and a Cu chip having a size of 2 mm ⁇ 2 mm and a thickness of 0.5 mm is mounted, and then nitrogen is added.
  • a sample was prepared by reflow heat treatment at a peak temperature of 160 ° C. in an atmosphere.
  • a reflow simulator (Malcom: SRS-1C) was used as the heat treatment apparatus. The temperature profile increased from 1.5 ° C / second to 120 ° C from the start of heat treatment (normal temperature), gradually increased from 120 ° C to 135 ° C over 110 seconds, and then increased at 2.0 ° C / second.
  • the conditions of heating and holding at a peak temperature of 160 ° C. for 15 seconds were employed.
  • a screen printer (Microtech: MT-320TV) was used for forming the print pattern.
  • the printing mask is made of metal and the squeegee is made of urethane.
  • the mask has an opening size of 2 mm ⁇ 3.5 mm and a thickness of 0.1 mm.
  • the printing conditions were a speed of 50 mm / second, a printing pressure of 0.1 MPa, a squeegee pressure of 0.2 MPa, a back pressure of 0.1 MPa, an attack angle of 20 °, a clearance of 0 mm, and a printing frequency of once.
  • the chip bonding strength in the shear direction of the sample prepared above was measured at a pushing speed of 10 mm / min with a push-pull gauge and converted to a value per unit area of 15.4 MPa. Met. Further, after heating the sample prepared above to 260 ° C. on a hot plate and holding it for 3 minutes, the chip bonding strength in the shear direction was measured by the same method as described above, and converted to a value per unit area. .35 MPa. Therefore, it was confirmed that the sample had heat resistance capable of maintaining the bonding strength even when heated at 260 ° C. In addition, being able to hold
  • maintain joining strength means showing the joining strength of 0.20 Mpa or more.
  • Examples 2 to 10, Comparative Examples 1 and 2 Using a metal filler component in which the mixing ratio of the first metal particle A and the second metal particle A is changed, a solder paste is produced in the same manner as in Example 1, and the chip bonding strength is measured in the same manner as in Example 1. did. The results are shown in Examples 2 to 5 in Table 1 and Comparative Example 1. Further, using each of the metal filler components having the same mixing ratio as in Examples 1 to 5, the temperature profile at the time of joining the Cu chip was raised from the start of heat treatment (room temperature) to 120 ° C. at 1.5 ° C./second. Table 6 shows the results obtained by gradually increasing the temperature from 120 ° C. to 135 ° C.
  • Example 11 to 20 Using a metal filler component in which the mixing ratio of the first metal particle B and the second metal particle B is changed, a solder paste is produced in the same manner as in Example 1, and at a peak temperature of 160 ° C. or 180 ° C. A reflow heat treatment (similar to Examples 1 to 10) was performed, and the bonding strength was measured in the same manner. The results are shown in Examples 11 to 20 in Table 2. From Table 2, it can be seen that Examples 11 to 20 containing the first metal particles B exhibit a bonding strength of 0.20 MPa or more even when heated to 260 ° C., and exhibit heat resistance that maintains the bonded state.
  • Example 21 A lead-free solder produced in Example 2 was printed on a Cu electrode of a printed circuit board made of a high heat-resistant epoxy resin glass cloth, and 0603 size multilayer ceramic chip capacitor (hereinafter abbreviated as 0603C, or simply referred to as a mounted component). ) was then subjected to reflow heat treatment under the conditions described in Example 1 to prepare a sample.
  • 0603C 0603 size multilayer ceramic chip capacitor
  • the sample prepared above was heated to 105 ° C. on a hot plate, the underfill was applied so as not to cover the upper part of the mounted component, and cured in an oven at 165 ° C. for 2 hours.
  • a transparent mold resin was applied to the upper part and the periphery of the mounted component and cured in an oven at 150 ° C. for 4 hours.
  • reflow heat treatment was performed at a peak temperature of 260 ° C. in a nitrogen atmosphere.
  • a reflow simulator (Malcom: SRS-1C) was used as the heat treatment apparatus.
  • the temperature profile was as follows: from heat treatment start (room temperature) to 150 ° C. at a rate of 1.5 ° C./second, gradually increasing from 150 ° C. to 210 ° C. over 100 seconds, then from 210 ° C. to 260 ° C. The temperature was raised at a rate of 0.0 ° C./second, and the conditions were maintained at a peak temperature of 260 ° C. for 15 seconds.
  • Example 4 A conventional representative lead-free solder Sn-3.0Ag-0.5Cu was evaluated in the same manner as in Example 21. However, only the temperature profile when mounting 0603C is different, the temperature is increased from the start of heat treatment (room temperature) to 140 ° C at 1.5 ° C / second, and gradually from 140 ° C to 170 ° C over 100 seconds. The temperature was raised from 170 ° C. to 250 ° C. at a rate of 2.0 ° C./second and maintained at a peak temperature of 250 ° C. for 15 seconds. The results are shown in Table 3.
  • the lead-free solder using the metal filler of the present invention is capable of joining parts at low temperatures, and does not melt and flow out even in subsequent reflow, and is a material with excellent heat resistance. Recognize.
  • Example 22 The 1st metal particle A and the 2nd metal particle A were mixed by mass ratio 100: 186, and it was set as the metal filler component. Next, 90% by mass of the metal filler component and 10% by mass of the flux (B) were mixed, and a solder paste was produced in the same procedure as in Example 1. The solder paste is printed and applied onto a Cu electrode of a printed circuit board made of high heat-resistant epoxy resin glass cloth, and after mounting a 1005 size resistor chip (hereinafter referred to as 1005R, or simply referred to as a mounted component), the peak temperature in a nitrogen atmosphere Reflow heat treatment was performed at 160 ° C. to prepare a sample.
  • 1005R 1005 size resistor chip
  • the obtained sample is embedded in epoxy resin, and the cross-section of the mounted component is observed by polishing the cross-section. Counts the number of metal particles (floating particles) present. The results are shown in Table 4. In addition, the number of suspended particles shown in Table 4 is an average of values obtained by counting suspended particles at six joint portions of 1005R.
  • Example 23 to 24 The same evaluation was performed using the first metal particle B or the first metal particle C instead of the first metal particle A in Example 22.
  • the results are shown in Table 4.
  • the first metal particles C having an average particle diameter of 2.7 ⁇ m are used, many suspended particles are observed in the flux layer of the solder upper layer of the joint.
  • the first metal particles B having an average particle diameter of 8.1 ⁇ m or the first metal particles A having an average particle diameter of 15.1 ⁇ m are used, there are few floating particles generated in the flux layer. I understand.
  • the average particle diameter of the metal particles used is small (for example, 2.7 ⁇ m)
  • the average particle diameter is, for example, 8.1 ⁇ m and 15.1 ⁇ m
  • floating particles are generated in the flux layer. It turns out that the advantage that it is hard to do is acquired.
  • Examples 25 to 27 The first metal particles A and the second metal particles B were mixed at a mass ratio of 100: 186 to obtain a metal filler component. Next, 89.5 mass% of the metal filler component and 10.5 mass% of the flux (B) were mixed, and a solder paste was produced in the same procedure as in Example 1. The obtained solder paste was printed and applied onto an alumina substrate, and the adhesive strength was measured using a tackiness tester (manufactured by Malcolm) TK-1. The results are shown in Example 25 in Table 5. The adhesive strength was measured at 5 points, and the average value is shown in Table 5.
  • the solder paste was produced in the procedure similar to Example 1, and adhesive force was measured similarly.
  • the results are shown in Examples 26 and 27 in Table 5, respectively. Accordingly, when the average particle size is 8.1 ⁇ m and 15.1 ⁇ m, for example, compared to the case where the average particle size of the metal particles used is as large as the metal particle D (average particle size: 30.2 ⁇ m). It can be seen that the advantage that the adhesive strength is high and the adhesive strength as a paste is strong can be obtained.
  • Example 28 and 29 The 1st metal particle A and the 2nd metal particle A were mixed by mass ratio 100: 186, and it was set as the metal filler component. Next, 90% by mass of the metal filler component and 10% by mass of the flux (B) were mixed, and a solder paste was produced in the same procedure as in Example 1. Using the obtained paste, similarly to Example 1 (4), a reflow heat treatment was performed at a peak temperature of 160 ° C. in a nitrogen atmosphere to prepare a Cu chip bonded substrate, and the bonding strength at room temperature and 260 ° C. heating was obtained. It was measured. The results are shown in Example 28 of Table 6.
  • Example 29 of Table 6 The results are shown in Example 29 of Table 6.
  • Example 28 and Comparative Example 5 in Table 6 or Example 29 and Comparative Example 6 are compared, the second metal particles are compared with the combination of Bi-42Sn as the second metal particles and Cu powder. It can be seen that the bonding strength at room temperature is significantly better when the combination of Bi-42Sn and the first metal particles A is used.
  • third metal particles 1.0 kg of Ag particles (purity 99% by mass or more), 2.0 kg of Bi particles (purity 99% by mass or more), 1.5 kg of Cu particles (purity 99% by mass or more), 2.0 kg of In particles (Purity 99% by mass or more), Sn particles 3.5 kg (Purity 99% by mass or more) (namely, the target element composition is Ag: 10% by mass, Bi: 20% by mass, Cu: 15% by mass, In: 20% by mass) , And Sn: 35% by mass) were put into a graphite crucible and heated to 1400 ° C. with a high-frequency induction heating apparatus in a helium atmosphere of 99% by volume or more to melt.
  • this molten metal is introduced into the spray tank in the helium gas atmosphere from the tip of the crucible, and then helium gas (purity 99 volume% or more, oxygen concentration 0.1 volume) from a gas nozzle provided in the vicinity of the crucible tip.
  • Atomization was performed by ejecting less than% and a pressure of 2.5 MPa to produce third metal particles.
  • the cooling rate at this time was 2600 ° C./second.
  • the obtained third metal particles were spherical when observed with a scanning electron microscope (manufactured by Hitachi, Ltd .: S-2700).
  • Example 7 the first metal particles A and the third metal particles were mixed at a mass ratio of 100: 186 to obtain a metal filler component.
  • 88.4% by mass of the metal filler component and 11.6% by mass of the flux (B) were mixed, and a solder paste was produced in the same procedure as in Example 1.
  • a reflow heat treatment was performed at a peak temperature of 160 ° C. in a nitrogen atmosphere to prepare a Cu chip bonded substrate, and the bonding strength at room temperature and 260 ° C. heating was obtained. It was measured. The results are shown in Comparative Example 7 in Table 7.
  • Example 1 a reflow heat treatment was performed at a peak temperature of 160 ° C. in a nitrogen atmosphere to prepare a Cu chip bonded substrate, and the bonding strength when heated at normal temperature and 260 ° C. was measured. The results are shown in Comparative Example 8 in Table 7.
  • the metal filler of the present invention and the lead-free solder containing the metal filler are used for a plurality of heat treatments in a subsequent process (for example, a solder material used for an electronic device such as a component-embedded substrate and a package, and further, for example, a conductive adhesive). And can be mounted at low temperature.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)
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Abstract

L'invention consiste en une charge métallique comprenant un mélange d'une première particule métallique et d'une seconde particule métallique. Ladite première particule métallique consiste en une particule d'alliage de cuivre comprenant un Cu en tant que composant principal, lequel consiste en un élément présent dans son rapport massique le plus élevé; et comprenant en outre du In et du Sn; ladite seconde particule métallique consiste en une particule d'alliage de Bi comprenant de 40 à 70% en masse de Bi, et de 30 à 60% en masse d'au moins une sorte de métal choisi parmi Ag, Cu, In et Sn; et la quantité de ladite seconde particule métallique par rapport à 100 parties en poids de la première particule métallique est comprise dans une plage allant de 40 à 300 parties en poids. Cette invention concerne également un brasage sans plomb comprenant ladite charge métallique, une structure de connexion formée à l'aide dudit brasage sans plomb et d'un substrat de montage de composants possédant ladite structure de connexion.
PCT/JP2010/052880 2009-02-25 2010-02-24 Charge métallique, brasage sans plomb de connexion basse température, et structure de connexion WO2010098357A1 (fr)

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KR1020117017424A KR101230195B1 (ko) 2009-02-25 2010-02-24 금속 충전재, 저온 접속 납프리 땜납 및 접속 구조체
CN201080007347.9A CN102317031B (zh) 2009-02-25 2010-02-24 金属填料、低温连接无铅焊料、及连接结构体

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JP2012125791A (ja) * 2010-12-15 2012-07-05 Asahi Kasei E-Materials Corp 金属フィラー及びこれを含む鉛フリーはんだ
JP2013163185A (ja) * 2012-02-09 2013-08-22 Asahi Kasei E-Materials Corp 金属フィラー、はんだペースト、及び接続構造体
JP2013258254A (ja) * 2012-06-12 2013-12-26 Koki:Kk レーザー加熱工法による電子デバイスの製造方法
CN111822698A (zh) * 2019-04-22 2020-10-27 松下电器产业株式会社 接合结构体和接合材料
US11618108B2 (en) * 2018-09-28 2023-04-04 Tamura Corporation Molded solder and molded solder production method

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CN104043911B (zh) * 2014-06-27 2017-08-08 深圳市汉尔信电子科技有限公司 一种可形成均匀组织焊点的无铅焊料及其焊接方法
CN106636829B (zh) * 2015-11-04 2018-04-06 中国科学院理化技术研究所 自封装液态金属笔及制作方法
WO2018134673A1 (fr) * 2017-01-20 2018-07-26 レノボ・シンガポール・プライベート・リミテッド Procédé de liaison par brasage et joint à brasure tendre
WO2019117041A1 (fr) * 2017-12-11 2019-06-20 株式会社弘輝 Pâte à braser, structure de joint et procédé de production d'une structure de joint

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WO2008056676A1 (fr) * 2006-11-06 2008-05-15 Victor Company Of Japan, Limited Pâte à braser sans plomb, carte de circuit électronique utilisant cette pâte à braser sans plomb, et procédé de fabrication de carte de circuit électronique
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Publication number Priority date Publication date Assignee Title
JP2012125791A (ja) * 2010-12-15 2012-07-05 Asahi Kasei E-Materials Corp 金属フィラー及びこれを含む鉛フリーはんだ
JP2013163185A (ja) * 2012-02-09 2013-08-22 Asahi Kasei E-Materials Corp 金属フィラー、はんだペースト、及び接続構造体
JP2013258254A (ja) * 2012-06-12 2013-12-26 Koki:Kk レーザー加熱工法による電子デバイスの製造方法
US11618108B2 (en) * 2018-09-28 2023-04-04 Tamura Corporation Molded solder and molded solder production method
CN111822698A (zh) * 2019-04-22 2020-10-27 松下电器产业株式会社 接合结构体和接合材料
CN111822698B (zh) * 2019-04-22 2023-07-14 松下控股株式会社 接合结构体和接合材料

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