WO2017018155A1 - Fil de soudure revêtu et son procédé de fabrication - Google Patents

Fil de soudure revêtu et son procédé de fabrication Download PDF

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Publication number
WO2017018155A1
WO2017018155A1 PCT/JP2016/070135 JP2016070135W WO2017018155A1 WO 2017018155 A1 WO2017018155 A1 WO 2017018155A1 JP 2016070135 W JP2016070135 W JP 2016070135W WO 2017018155 A1 WO2017018155 A1 WO 2017018155A1
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Prior art keywords
solder wire
coated
solder
mass
coating film
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PCT/JP2016/070135
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English (en)
Japanese (ja)
Inventor
小林　宏
恭子 宮内
山辺　秀敏
Original Assignee
住友金属鉱山株式会社
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Priority claimed from JP2015212063A external-priority patent/JP6471676B2/ja
Application filed by 住友金属鉱山株式会社 filed Critical 住友金属鉱山株式会社
Priority to CN201680040706.8A priority Critical patent/CN107848076A/zh
Priority to EP16830260.2A priority patent/EP3330039A4/fr
Publication of WO2017018155A1 publication Critical patent/WO2017018155A1/fr

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    • 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
    • B23K35/28—Selection of soldering or welding materials proper with the principal constituent melting at less than 950 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
    • B23K35/40—Making wire or rods for soldering or welding
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C11/00—Alloys based on lead
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/04—Alloys based on zinc with aluminium as the next major constituent

Definitions

  • the present invention relates to a coated solder wire used for manufacturing a semiconductor device and a method for manufacturing the same.
  • soldering is generally employed when bonding metal materials together or when bonding electronic components such as semiconductor elements to a printed circuit board.
  • Solder materials used for soldering are formed into various shapes such as wires, ribbons, sheets, preform materials (punching materials), balls, and fine powders.
  • Solder material is easily oxidized in the presence of oxygen, and an oxide film is formed on the surface during storage.
  • the oxidation proceeds and the oxide film becomes thick. This causes joint defects such as voids.
  • the oxide film becomes thicker. If such a thick oxide film is present at the bonding interface, problems such as poor conduction and poor bonding occur at the bonded portion.
  • the surface treatment using the atmospheric pressure plasma CVD method can form a dense coating film at a relatively low cost, so that not only the antioxidant effect is high but also the film forming material diffuses into the room. It has attracted attention because of its superior safety.
  • Japanese Patent Application Publication No. 2004-510571 discloses that a spray liquid coating forming material made of an organosilicon compound is introduced into an atmospheric pressure plasma discharge, and a substrate such as a metal is exposed to the spray coating forming material. Discloses a method of forming a coating (coating film) made of polydimethylsiloxane or the like.
  • the plasma of the reactive gas and the activation of the spray coating forming material that is atomized are performed at the same time, so the activation of the spray coating forming material becomes non-uniform and the entire surface of the substrate is dense. It is difficult to form a uniform coating film uniformly. Further, this method is not intended to prevent the oxidation of the surface of the solder material. Therefore, the behavior of the coating film at the time of melting of the solder material, and the wettability and joining property due to the presence of the coating film are considered. No consideration is given to the effects of.
  • Japanese Patent Application Laid-Open No. 2014-195831 discloses radicalization of an organosilicon compound by mixing and spraying an organosilicon compound together with a carrier gas in a plasma gas under atmospheric pressure.
  • a method for producing a coated solder material is disclosed in which a coating film made of polysiloxane having a thickness of 4 nm to 200 nm is formed by reacting with a metal present on the surface of the solder material while polymerizing the compound.
  • a dense coating film can be uniformly formed over the entire surface of the solder material while maintaining the basic skeleton of the organosilicon compound. it can. For this reason, in this method, it is possible to prevent the progress of oxidation during long-term storage and melting without impairing the wetting and joining properties of the solder material.
  • the present invention can prevent oxidation of the surface during long-term storage and melting by forming a dense coating film uniformly over the entire surface of the solder wire by a single treatment, and It is an object to efficiently provide a coated solder wire that is further superior to the conventional one in terms of wetting spreadability and bondability by manufacturing on an industrial scale.
  • the coated solder wire of the present invention comprises a solder wire and a coated film containing a phosphorus-containing compound formed on the surface of the solder wire as a main component and having a thickness in the range of 1 nm to 100 nm. To do.
  • the thickness of the coating film is preferably in the range of 3 nm to 80 nm, and more preferably in the range of 5 nm to 50 nm.
  • the difference between the maximum value and the minimum value of the thickness of the coating film is preferably 2.5 nm or less, more preferably 2.0 nm or less, and further preferably 1.5 nm or less.
  • the maximum diameter in a plan view of the bonding solder obtained by bonding at a bonding temperature of 340 ° C. to 350 ° C. using the coated solder wire is determined.
  • the aspect ratio calculated by the formula ((X + Y) / 2) / Z is and a C has the solder wire the same composition as, and the solder wire uncoated, the aspect ratio obtained in the same manner as in the coating solder wire when the a n, the aspect ratio of the yet-coated solder wire it can be used the ratio of the aspect ratio a C of the coating solder wire for a n (a C / a n ).
  • the feature of the coated solder wire of the present invention is that the ratio (A C / A n ) is in the range of 1.6 to 3.0, and exhibits extremely high wet spreadability with respect to the uncoated solder wire. Can be mentioned.
  • the ratio (A C / A n ) is more preferably in the range of 1.7 to 2.8, and still more preferably in the range of 1.8 to 2.5.
  • the present invention can be arbitrarily applied to solder wires having various compositions.
  • the present invention is selected from the group consisting of 80% by mass or more of Pb and Sn, Ag, Cu, In, Te, and P.
  • the present invention is suitably applied to a solder wire that contains one or more second elements and contains a solder alloy having a total content of Pb and the second element of 95% by mass or more.
  • the present invention contains 80% by mass or more of Sn and one or more second elements selected from the group consisting of Ag, Sb, Cu, Ni, Ge, and P, and Sn and It is suitably applied to a solder wire made of a solder alloy having a total content of two elements of 95% by mass or more.
  • the present invention provides one or more third elements selected from the group consisting of 90% by mass or more of Zn, 2.0% by mass or more and 9.0% by mass or less of Al, and Ag, Ge, and P.
  • the Ag content is 0.1% by mass or more and 4.0% by mass or less
  • the Ge content is 0.01% by mass or more and 2.% by mass.
  • it contains 00 mass% or less and P, it applies suitably to the solder wire which consists of a solder alloy whose P content is 0.5000 mass% or less.
  • the method for producing the coated solder wire of the present invention is as follows.
  • a radicalization step in which a reaction gas plasmified under atmospheric pressure and an organophosphorus compound introduced via a carrier gas are mixed and radicalized to form a radicalized organophosphorus compound.
  • a reaction region forming step defined by a spiral gas flow to form a reaction region in which the radicalized organophosphorus compound is uniformly dispersed;
  • a solder wire is conveyed, and the radicalized organophosphorus compound is reacted with a metal on the surface of the solder wire, whereby a phosphorus-containing compound having a thickness of 1 nm to 100 nm on the surface of the solder wire is a main component.
  • Forming a coating film containing as a coating process It is characterized by providing.
  • the reaction region is preferably formed by mixing the radicalized organophosphorus compound in a spiral gas flow introduced in advance.
  • the spiral gas flow can be formed by at least one selected from the group consisting of argon, helium, nitrogen, oxygen, and air.
  • organic phosphorus compound examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tripentyl phosphate, bis (2-ethylhexyl) hydrogen phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, phosphorous acid At least one selected from tributyl, tripentyl phosphite, bis (2-nonylphenyl) hydrogen phosphite, and triphenyl phosphite can be used.
  • reaction gas at least one selected from the group consisting of argon, helium, nitrogen, oxygen, and air can be used.
  • carrier gas at least one selected from argon, helium, and nitrogen can be used.
  • the organophosphorus compound is preferably radicalized by an atmospheric pressure plasma polymerization treatment apparatus.
  • the amount of the organophosphorus compound introduced into 1 m of the solder wire is preferably in the range of 0.005 g to 0.560 g.
  • the amount of the organophosphorus compound introduced is more preferably in the range of 0.016 g to 0.450 g, and still more preferably in the range of 0.028 g to 0.280 g.
  • the solder wire conveyance speed in the coating step is preferably 1 m / min to 100 m / min, more preferably 5 m / min to 80 m / min, and 10 m / min to 50 m / min. Is more preferable.
  • a coated solder wire in which a dense coating film containing a phosphorus-containing compound as a main component is uniformly formed over the entire surface of the solder wire.
  • the coated solder wire of the present invention employs a phosphorus-containing compound as a main component of the coating film, thereby comparing with a conventional uncoated solder wire or a solder wire having a coating film made of polysiloxane. , Better wet spreadability and bondability.
  • such a coated solder wire can be obtained efficiently by a single treatment.
  • FIG.1 (a) is a schematic perspective view for demonstrating the manufacturing method of the covering solder wire of this invention
  • FIG.1 (b) is sectional drawing of the covering solder wire obtained by this manufacturing method.
  • . 2 (a-1) to (c-1) are schematic perspective views for explaining the conventional method of manufacturing a coated solder wire step by step
  • FIGS. 2 (a-2) to (c-). 2) is a cross-sectional view of the coated solder wire at each stage.
  • polysiloxane is used as a material for the coating film.
  • the coating film using polysiloxane not only has the function of preventing the progress of oxidation of the solder wire during long-term storage and melting, but also has the same wettability as before. Adds spreadability and bondability.
  • solder wire is required to further improve wettability and bondability.
  • a coated solder wire having a coating film using polysiloxane can sufficiently meet such requirements. Can not.
  • the present inventors have further improved the wettability and bonding properties of solder wires by using a phosphorus-containing compound instead of polysiloxane as the material of the coating film. The knowledge that is seen.
  • the organophosphorus compound used as the coating film material is radicalized in advance to form a reaction region in which the radicalized organophosphorus compound is uniformly dispersed, and a solder wire is formed in the reaction region.
  • the present invention has been completed based on these findings.
  • the present invention will be described in detail by dividing it into “1. coated solder wire”, “2. manufacturing method of coated solder wire”, and “3. die bonding method using coated solder wire”.
  • the coated solder wire of the present invention is not limited by the diameter of the solder wire used as the base material. However, in the following, a solder wire having a diameter of 0.3 mm to 1.0 mm that is generally used is used. The case where it is used as a base material will be described as an example.
  • the coated solder wire of the present invention includes a solder wire and a coated film containing a phosphorus-containing compound formed on the surface of the solder wire.
  • This coating film has a thickness in the range of 1 nm to 100 nm.
  • solder Wire the composition of the solder wire is arbitrary, and the present invention can be applied to solder wires having various compositions. However, when the solder wire having the following composition is used, the effects of the present invention are suitably exhibited.
  • the composition of the solder wire can be determined by ICP emission spectroscopic analysis.
  • Pb-based solder wires are mainly composed of lead (Pb), tin (Sn), silver (Ag), copper (Cu), indium (In), tellurium (Te), and phosphorus (P And a solder alloy containing at least one second element selected from the group consisting of:
  • Pb as a main component means that content of Pb with respect to the whole solder alloy is 80 mass% or more.
  • Pb-based solder wires are extremely versatile and have been used for various purposes.
  • the use of Pb has been restricted in consideration of the effects on the human body and the environment, but due to its versatility and ease of use, as a high temperature solder, in some applications such as joining power devices, But it continues to be used.
  • the total content of Pb and the second element is 95% by mass or more, preferably 97% by mass or more in total. If the total content of Pb and the second element is less than 95% by mass, it is difficult to obtain the above characteristics.
  • the Pb content is preferably 80% by mass or more and less than 98% by mass, more preferably 85% by mass or more and less than 98% by mass. Further, the content of the second element is preferably 2% by mass or more and less than 15% by mass, more preferably 2% by mass or more and less than 12% by mass.
  • an element other than Pb and the second element may be contained according to the application and purpose.
  • a third element include nickel (Ni), germanium (Ge), cobalt (Co), antimony (Sb), and bismuth (Bi).
  • the content of the third element is preferably 5.0% by mass or less, more preferably 4.5% by mass or less. If the content of the third element exceeds 5.0% by mass, it may not be possible to obtain desired characteristics due to the relationship between the content of Pb and the second element.
  • Sn-based solder wire contains Sn as a main component and contains one or more second elements selected from the group consisting of Ag, Sb, Cu, Ni, Ge, and P. Consists of Here, Sn as a main component means that the Sn content with respect to the entire solder alloy is 80% by mass or more.
  • Such Sn-based solder wires have a low melting point and can be preferably applied to applications such as semiconductor devices, and are used as so-called “lead-free solder”.
  • lead-free means that the content is less than 0.01% by mass even when lead is not contained at all or is contained as an inevitable impurity.
  • the total content of Sn and the second element is 95% by mass or more, preferably 97% by mass or more in total. If the total content of Sn and the second element is less than 95% by mass, the above characteristics cannot be obtained.
  • the Sn content is preferably 80% by mass or more and less than 98% by mass, more preferably 90% by mass or more and less than 98% by mass.
  • the content of the second element is preferably 1% by mass or more and less than 10% by mass, more preferably 2% by mass or more and less than 7% by mass.
  • Sn-based solder wires may contain elements other than Sn and the second element (third element) depending on the application and purpose.
  • the third element include In, Co, and Bi.
  • the content of the third element is preferably 5.0% by mass or less, more preferably 3.0% by mass or less. When the content of the third element exceeds 5.0% by mass, desired characteristics cannot be obtained in relation to the contents of Sn and the second element.
  • Zn-based solder wire is composed of 90% by mass or more of zinc (Zn), 2.0% by mass or more and 9.0% by mass or less of aluminum (Al), and further Ag, Ge, and P.
  • Zn zinc
  • Al aluminum
  • P gold
  • the P content is 0.01 mass% or more and 2.00 mass% or less, the P content is 0.5000 mass% or less.
  • Such a Zn-based solder wire has a high melting point and can be preferably applied to applications such as semiconductor parts such as power devices, and is used as a so-called “high temperature lead-free solder”.
  • lead-free means that the content is less than 0.01% by mass even when lead is not contained at all or as an inevitable impurity.
  • the Zn content is 90% by mass or more and the Al content is 2.0% by mass or more and 9.0% by mass or less.
  • the reason for this composition range is as follows. It is. Zn and Al can form a eutectic alloy that becomes a eutectic point when the Al content is 5.0% by mass, and can form a solder alloy having excellent flexibility and workability. Furthermore, since the eutectic point temperature of the Zn—Al solder alloy is 381 ° C., the Zn—Al solder alloy has a melting point suitable for high temperature use, particularly for joining SiC or the like. Although it is an excellent Zn—Al solder alloy as described above, in order to further improve and adjust various properties, the Zn—Al solder alloy of the present invention includes at least one selected from the group consisting of Ag, Ge and P. It can be included.
  • Ag is excellent in reactivity, as can be seen from the fact that it is plated on the substrate, it spreads well on the joint surface such as Cu or Ni. In addition, since much O can be dissolved in the alloy, the effect of improving wettability is very high. Therefore, Ag is mainly contained when it is desired to improve wettability and bondability.
  • the content of Ag is not less than 0.1% by mass and not more than 4.0% by mass. When the content of Ag is less than 0.1% by mass, the content is too small and the effect of the addition does not substantially appear. On the other hand, when the Ag content exceeds 4.0% by mass, the content is too high, and a metal compound is generated more than permissible, or a melting separation phenomenon occurs, which is not preferable. .
  • the effect obtained by containing Ge is mainly improvement of wettability.
  • the mechanism of the wettability improvement effect of Ge is different from that of Ag.
  • Ge has a low specific gravity, so it is likely to exist near the surface in the molten solder.
  • Ge existing in the vicinity of the surface of the solder serves as a parent phase, so that oxidation of Al or Zn that is easily oxidized is suppressed.
  • the addition of Ge improves wettability during bonding.
  • Ge has the effect of suppressing the oxidation of the parent phase and preventing the progress of the oxidation of the solder.
  • the content of Ge having such excellent effects is 0.01% by mass or more and 2.00% by mass or less.
  • the content is too small, and the effect of the addition does not substantially appear.
  • the content of Ge exceeds 2.00 mass%, the brittleness of the phase containing Ge becomes remarkable, so that the workability and stress relaxation properties of the solder alloy are lowered, which is not preferable.
  • the P content is preferably 0.5% by mass or less. Since P is very reducible, the effect of improving the wettability can be obtained if a trace amount is contained, but the effect of improving the wettability does not change so much even if contained in excess of 0.5% by mass. Pd and P-containing oxide gas are generated in large quantities due to inclusion, increasing the void fraction in the solder, segregating by forming a brittle phase of P, making the solder joint brittle and joining reliability May be reduced.
  • the coating film of the present invention is mainly composed of a phosphorus-containing compound.
  • the phosphorus-containing compound refers to a polymer containing P in the structure.
  • the type of the polymer containing phosphorus which is a phosphorus-containing compound, is arbitrary, but the viewpoint of preventing the progress of oxidation on the surface of the solder wire, and the wettability and bondability at the time of bonding to the substrate are further improved.
  • the main component is polyphosphoric acid, polyphosphoric acid ester, polyphosphoric acid salt, and a three-dimensional cross-linked product thereof represented by the following formula.
  • Such a coating film mainly made of a polymer containing P has high density, and can thereby impart excellent oxidation resistance to the solder wire.
  • it when joining to the base material, it has the property that P is oxidized and vaporized as a gas and does not remain in the joint, so that wetting and spreading of the joint by solder is possible. And the bondability can be further improved.
  • the coating film of the present invention is mainly composed of a phosphorus-containing compound.
  • the coating film includes a phosphorus-containing compound as a main component because of the nature of the atmospheric pressure plasma polymerization method.
  • carbon components, hydrocarbons and the like may be included.
  • an optional additive component such as an antioxidant, conductive fine particles, or a coupling agent can be included.
  • the content of components other than the phosphorus-containing compound in the coating film is preferably 10% by mass or less, and more preferably 5% by mass or less.
  • the thickness of the coating film is controlled to 1 nm to 100 nm, preferably 3 nm to 80 nm, more preferably 5 nm to 50 nm. If the thickness of the coating film is less than 1 nm, the progress of oxidation on the surface of the solder wire cannot be sufficiently suppressed, and there may be problems such as deterioration of wet spreadability, bonding property, and generation of voids. . On the other hand, if the thickness of the coating film exceeds 100 nm, the progress of oxidation on the surface of the solder wire can be suppressed, but due to the effect of the coating film, wetting spreadability and bonding property decrease, voids (voids) are generated. May occur.
  • the thickness of the coating film is determined by observing each cross section with a transmission electron microscope (TEM) after cutting the coated solder wire along the length direction at three or more positions in the circumferential direction. Can be sought.
  • TEM transmission electron microscope
  • the coating film is also excellent in thickness uniformity.
  • the difference between the maximum value and the minimum value of the thickness (diameter direction dimension) of the coating film is set to be equal to 2. over the entire coated solder wire (length direction and circumferential direction). It is possible to control within 5 nm, preferably within 2.0 nm, more preferably within 1.5 nm. For this reason, it can be said that the coated solder wire of the present invention has extremely small variations in characteristics such as oxidation resistance, wettability, and bondability.
  • the coating film constituting the coated solder wire of the present invention is formed extremely thin, it is firmly bonded to the metal on the surface of the solder wire and has excellent thickness uniformity. Can be evaluated. Therefore, it is possible to suppress the progress of oxidation on the surface of the solder wire, and thereby it is possible to effectively suppress the wetting and spreading property of the solder wire and the bonding and the generation of voids.
  • the coating film is mainly composed of a phosphorus-containing compound
  • the spreadability of the coated solder wire of the present invention is further improved in comparison with the coated solder wire in which the coating film is composed of polysiloxane. .
  • the roundness and aspect ratio of the joint solder obtained by die bonding described later using this coated solder wire are used as an evaluation of the wettability of the coated solder wire.
  • the heater temperature (joining temperature) of the die bonder is set to 340 ° C. to 380 ° C., preferably 340 ° C. to 350 ° C., which is 50 ° C. higher than the melting point of the solder wire. Then, the coated solder wire is supplied, and the coated solder wire is melted to obtain a joining solder. In addition, as a comparison object, a bonding solder is obtained for uncoated solder wires by the same die bonding.
  • the length of the joint solder sample in the direction of the largest diameter in plan view with the observation means such as a microscope is measured and set it as the maximum diameter X.
  • the diameter in the direction orthogonal to the extending direction of the maximum diameter X is measured and set as the diameter Y.
  • the height of the joining solder is measured and set as a height Z.
  • the roundness is obtained from the measured value for each sample by the formula: “Y / X”.
  • the uncoated solder wire has a roundness of 0.87 or more at a joining temperature of 360 ° C. to 380 ° C., but the roundness rapidly deteriorates at a joining temperature of 340 ° C. to 350 ° C.
  • the coated solder wire of the present invention has a roundness of 0.87 or more, preferably 0.88 or more, in any case where the joining temperature is in the range of 340 ° C. to 380 ° C. It becomes.
  • the aspect ratio is obtained from the measured value for each sample by the formula: “((X + Y) / 2) / Z”.
  • the aspect ratio A C for coating the solder wire of the present invention in the junction temperature of 360 ° C. ⁇ 380 ° C., a good and a range of about 8.0-11.0, and junction temperature 340 Even at a temperature of 350 ° C. to 350 ° C., the range of about 7.0 to 10.8 is favorable. That is, the coated solder wire of the present invention has good wettability at a high bonding temperature, but can maintain good wettability with respect to a substrate such as a Cu substrate even when the bonding temperature is lowered. it can. Therefore, by die bonding using the coated solder wire of the present invention, it is possible to stably form a joint portion that exhibits wet spreadability and bondability equivalent to or better than conventional ones.
  • a bonding solder having a bonding temperature of 340 ° C. to 350 ° C. which clearly shows a difference from the conventional solder wire, is obtained as an index indicating the wet spreading property.
  • an aspect ratio determined for solder wire coating to a n employs a ratio of the aspect ratio a C covering the solder wire of the present invention (a C / a n). By using this ratio (A C / A n ), it becomes possible to appropriately evaluate the wetting and spreading property by changing the composition of the solder wire and bonding conditions other than the bonding temperature.
  • this ratio (A C / A n ) is preferably in the range of 1.6 to 3.0, more preferably in the range of 1.7 to 2.8, and 1.8 to More preferably, it is in the range of 2.5.
  • this ratio (A C / A n ) is less than 1.6, it cannot be said that the conventional solder wire is sufficiently superior.
  • this ratio (A C / A n ) exceeds 3.0, it cannot be applied as a bonding part as a bonding abnormality.
  • the coating film constituting the coated solder wire of the present invention is colorless and transparent and, as described above, has excellent thickness uniformity despite being extremely thin. There is almost no appearance defect such as a stain.
  • the manufacturing method of the coated solder wire of the present invention is as follows. (1) A reaction gas plasmified under atmospheric pressure and an organic phosphorus compound introduced through a carrier gas are mixed to radicalize the organic phosphorus compound to form a radicalized organic phosphorus compound. A radicalization step; (2) a reaction region forming step defined by a spiral gas flow to form a reaction region in which the radicalized organophosphorus compound is uniformly dispersed; (3) A phosphorus-containing compound having a thickness of 1 nm to 100 nm is formed on the surface of the solder wire by conveying the solder wire in the reaction region and reacting the radicalized organophosphorus compound with the metal on the surface of the solder wire. A coating step of forming a coating film containing as a main component; Is provided.
  • a dense coating film mainly containing a phosphorus-containing compound can be uniformly formed on a solder wire by a single treatment. Can be improved.
  • this manufacturing method uses an organic phosphorus compound that is normally liquid as the coating material, and because the coating film is formed by a dry method, it is not only easy to handle, but also safe. Also excellent.
  • radicalization process an organic phosphorus compound, which is a material of a phosphorus-containing compound that is a main component of the coating film, is introduced via a carrier gas, and is converted into a plasma at atmospheric pressure. And an organophosphorus compound, and radicalizing the organophosphorus compound to form a radicalized organophosphorus compound.
  • the atmospheric pressure plasma polymerization treatment is a technique that has been widely known
  • the atmospheric pressure plasma polymerization treatment used in the present invention is a chemical reaction that does not proceed under normal conditions. It is made to progress by the conversion.
  • Such an atmospheric pressure plasma polymerization process is characterized by high productivity because it is suitable for continuous processing, and has a feature that the processing cost is low because a vacuum apparatus is unnecessary, and the apparatus configuration can be simplified.
  • atmospheric pressure plasma examples include corona discharge, dielectric barrier discharge, RF discharge, microwave discharge, arc discharge, and the like, but any of them can be applied in the present invention without any particular limitation. For this reason, a known plasma generator can be used without any particular limitation as long as it can plasmify the reaction gas under atmospheric pressure. .
  • atmospheric pressure includes atmospheric pressure (1013.25 hPa) and atmospheric pressure in the vicinity thereof, and also includes atmospheric pressure within the range of changes in normal atmospheric pressure.
  • the organophosphorus compound can be instantly radicalized, so that the phosphorus-containing compound that mainly constitutes the coating film is applied to the entire surface of the solder wire while maintaining the basic skeleton of the organophosphorus compound. It becomes possible to form densely and uniformly.
  • a reaction gas, a carrier gas, and a coating material are supplied into the apparatus, and then the reaction gas is converted into plasma and coated. Since radicalization of the material is performed at the same time, radicalization of the coating material becomes non-uniform. As a result, the coating film does not become dense, and it is difficult to form the coating film uniformly on the entire surface of the solder wire.
  • the conditions for converting the reaction gas to plasma should be appropriately selected according to the plasma apparatus to be used, the thickness of the target coating film, and the like.
  • the generator output voltage is preferably in the range of 150 V to 350 V, more preferably 200 V to 330 V. If the generator output voltage is less than 150 V, the reaction gas cannot be sufficiently converted to plasma, and therefore the hydrocarbon may not be sufficiently radicalized. On the other hand, if it exceeds 350 V, there may be a problem such as damage to the apparatus.
  • Reactive gas is not particularly limited as long as it can be easily converted to plasma.
  • argon (Ar), helium (He), nitrogen (N 2 ), oxygen (O 2 ), Air or the like can be used.
  • These reaction gases may be used alone or in combination of two or more at a predetermined ratio. From the viewpoint of production cost, it is preferable to use nitrogen, oxygen, or a mixed gas thereof, particularly air.
  • Carrier gas is not particularly limited as long as it can transport the sprayed organophosphorus compound.
  • argon (Ar), helium (He), nitrogen (N 2 ), or the like can be used. These carrier gases may be used alone or in combination of two or more at a predetermined ratio. In addition, it is preferable to use nitrogen from a viewpoint of production cost.
  • an organophosphorus compound that is liquid at room temperature can be used as a coating material for forming a coating film.
  • At least one organophosphorus compound selected from tripentyl phosphite, bis (2-nonylphenyl) hydrogen phosphite, and triphenyl phosphite can be used.
  • trimethyl phosphate represented by the following formula is industrially suitable because it has a boiling point of 197 ° C., is a colorless and odorless liquid, exhibits high stability in air, and is easy to handle. Can be used.
  • the amount of the organophosphorus compound introduced into 1 m of the solder wire is preferably 0.005 g to 0.560 g, more preferably 0.016 g to 0.450 g, and 0.028 g to 0.005 g. More preferably, it is 280 g. If the amount of the organophosphorus compound introduced into the solder wire 1 m is less than 0.005 g, the thickness of the coating film may be 1 nm or less, or the thickness may vary. On the other hand, if the amount of the organophosphorus compound introduced into the solder wire 1 m exceeds 0.560 g, the thickness of the coating film may exceed 100 nm.
  • reaction region forming step is a step of forming a reaction region which is defined by a spiral gas flow and in which the radicalized organophosphorus compound obtained in the radicalization step is uniformly dispersed.
  • the radicalized organophosphorus compound is uniformly dispersed, and a reaction region in which the organophosphorus compound can react with the metal on the surface of the solder wire is formed in advance. It becomes important. As long as the organophosphorus compound in the reaction region is radicalized, its state is not limited, and any state of a monomer, a semipolymer, and a polymer may be used.
  • the reaction zone needs to be defined by a spiral gas flow. This is because the reaction between the metal on the surface of the solder wire and the radicalized organophosphorus compound proceeds simultaneously and at a similar reaction rate in the spiral gas flow in which the radicalized organophosphorus compound is uniformly dispersed. This is because the resulting coating film can be formed extremely uniformly.
  • the method for forming such a reaction region is not particularly limited.
  • it can be formed by introducing a spiral gas flow into the apparatus in advance and mixing the radicalized organophosphorus compound generated in the radicalization step with this spiral gas flow.
  • the radicalization step may be performed outside the apparatus, and the generated radicalized organophosphorus compound may be introduced into the apparatus as a spiral gas flow using a carrier gas.
  • the former method is preferably used in consideration of the fact that radicalized organophosphorus compounds are unstable and immediately return to ordinary organophosphorus compounds.
  • the spiral gas flow is, for example, at least one selected from the group of argon (Ar), helium (He), nitrogen (N 2 ), oxygen (O 2 ), and air, That is, it can be formed by introducing the same kind of gas as the carrier gas described above or a mixture of these gases with a radical organophosphorus compound generated outside the apparatus into the apparatus so as to flow spirally. .
  • Ar argon
  • He helium
  • N 2 nitrogen
  • oxygen oxygen
  • the spiral gas flow needs to be formed so that its cross-sectional area is larger than the diameter of the solder wire to be coated.
  • the velocity of the spiral gas flow (velocity with respect to the traveling direction and velocity with respect to the circumferential direction) is appropriately selected according to the thickness of the target coating film and the property of the solder wire (reactivity with the organophosphorus compound). It is necessary to do. For this reason, it is preferable to set the speed of the spiral gas flow after performing a preliminary test.
  • the coating process includes a phosphorus-containing compound as a main component on the surface of the solder wire by transporting the solder wire in the reaction region and reacting the radicalized organophosphorus compound with the metal on the surface of the solder wire, Preferably, it is a step of forming a coating film made of a phosphorus-containing compound and having a thickness in the range of 1 nm to 100 nm.
  • solder wire constituting the coated solder wire of the present invention is not particularly limited, and various types can be used. However, in order to fully exhibit the effects of the present invention, it is preferable to use a solder wire obtained by a molding method described below.
  • known means such as a resistance heating method, a reduction diffusion method, and a high-frequency dissolution method can be used.
  • a high-frequency dissolution method capable of efficiently melting in a short time is preferable.
  • a raw material melted by these methods is cast into a mold prepared in advance to form a solder mother alloy ingot having a predetermined shape. If oxygen is present at the time of melting or casting, not only the oxidation of the raw material proceeds, but also an oxide film is involved at the time of casting, resulting in a thick oxide film on the surface of the solder wire, or a rough surface roughness (Ra). It becomes. For this reason, it is preferable that the atmosphere at the time of melting the raw material is an inert gas atmosphere and the inert gas is circulated to the molten metal inlet of the mold at the time of casting.
  • solder wire When forming wire-shaped solder, a solder mother alloy ingot is formed by an extrusion method, a wire drawing method, or the like. For example, when forming by an extrusion method, it is necessary to select an appropriate extrusion temperature in accordance with the composition of the solder wire. This is because if the extrusion temperature is too high, the surface oxidation tends to proceed, and conversely if the extrusion temperature is too low, the solder wire is extruded in a hard state, and therefore it takes a long time to form. .
  • the extrusion is preferably performed in an inert gas, and more preferably performed while circulating the inert gas in a sealed state. This is because if oxygen is present during extrusion, the wire heated to the extrusion temperature will immediately oxidize.
  • the timing for performing the acid cleaning and polishing may be any timing after casting the solder mother alloy and before performing the predetermined processing, during processing, or after processing.
  • the type of acid used when performing acid cleaning is not particularly limited as long as it is appropriately selected depending on the composition of the solder wire, and both inorganic acid and organic acid can be used.
  • an inorganic acid which is inexpensive and has a large oxide film removing effect.
  • hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and the like can be used as the inorganic acid.
  • citric acid, oxalic acid, etc. can be used as the organic acid.
  • a strong acid due to the high dissolution rate of the solder wire in the acidic solution, partial dissolution proceeds and the surface roughness (Ra) increases or composition deviation occurs. There is. For this reason, it is preferable to use a weak acid that has a slow dissolution rate and is easy to handle. In acid cleaning, it is necessary to sufficiently consider the acid concentration, the cleaning time, the cleaning temperature, and the like.
  • the cleaning temperature is 20 ° C. and the cleaning time is 15 minutes.
  • the oxide film of the solder wire has the largest amount of dissolution immediately after contact with the acetic acid aqueous solution, and then gradually decreases and becomes saturated at a certain stage. Specifically, when an oxide film having a thickness of 100 ⁇ m is cleaned, the thickness of the oxide film is reduced from 20 ⁇ m to 30 ⁇ m in about 5 minutes and is reduced to about 10 ⁇ m in about 15 minutes.
  • the polishing method is not particularly limited.
  • the solder wire may be sandwiched between polishing papers, pressed with an appropriate force, and wound by pulling it while being pulled.
  • the reaction between the radicalized organophosphorus compound and the metal on the surface of the solder wire is carried out within the above-described reaction region. proceed. Specifically, as shown in FIG. 1A, the solder wire 2 serving as a base material is conveyed in the direction of arrow A through the substantially central portion of the reaction region 6 defined by the spiral gas flow 4. . At this time, since the radicalized organophosphorus compound 5 is uniformly dispersed in the reaction region 6, the organophosphorus compound 5 contacts the entire surface of the solder wire 2 equally by the action of the spiral gas flow 4. To do. As a result, the reaction between the radicalized organophosphorus compound 5 and the metal on the surface of the solder wire 2 proceeds simultaneously and at a similar reaction rate over the entire circumferential direction.
  • the radicalized organic phosphorus compound 5 exists in various states such as a monomer, a semipolymer, or a polymer. Therefore, as a reaction between the radicalized organophosphorus compound 5 and the metal on the surface of the solder wire 2, (I) a mode in which the radicalized organophosphorus compound 5 is polymerized after reacting with the metal on the surface of the solder wire 2; (Ii) a mode in which the radicalized organophosphorus compound 5 reacts with the metal on the surface of the solder wire 2 while being polymerized, or (iii) a mode in which the radicalized organophosphorus compound 5 reacts with the metal on the surface of the solder wire 2 after polymerization, Can be considered.
  • the method for producing a coated solder wire according to the present invention is not limited to any embodiment as long as the coated solder wire having the above-described coated film can be obtained.
  • the thickness of the coating film is adjusted to a range of 1 nm to 100 nm.
  • the thickness of such a coating film can be controlled not only by the amount of the organic phosphorus compound introduced as the coating material and the speed of the spiral gas flow, but also by the solder wire conveyance speed.
  • the solder wire conveyance speed in the coating step is preferably 1 m / min to 100 m / min, more preferably 5 m / min to 80 m / min, and 10 m / min to 50 m / min. More preferably.
  • the thickness of the coating film may be 1 nm or less, or the thickness may vary.
  • the coated solder wire of the present invention can be used for bonding various semiconductor elements and substrates, and specifically, a wide variety of semiconductors such as discrete, integrated circuit (IC) chips, modules, etc. It can be used for bonding the element and the substrate.
  • IC integrated circuit
  • high melting point particles those having a melting point higher by 50 ° C. or more than the melting point of the solder wire are preferably used.
  • metal particles such as Cu and Ni, oxide particles such as SiO 2 , SiC Such carbide particles can be used.
  • These high melting point particles preferably have an average particle size of 1 ⁇ m to 70 ⁇ m.
  • the content of the high melting point particles is preferably about 1% by mass to 40% by mass with respect to the solder wire.
  • a heater part is provided in a semi-sealed chamber provided with openings for supplying solder wires and semiconductor elements, and the substrate is transported to the heater part and heated.
  • an inert gas or forming gas (a gas obtained by mixing inert gas with hydrogen as a reducing gas) is circulated in the chamber.
  • a solder wire is supplied onto the substrate heated to a predetermined temperature, melted, and a semiconductor element is placed on the solder wire, and the substrate and the semiconductor element are joined by pressing.
  • the solder wire waits in a state in which a mixed gas of heated inert gas and air is sprayed at the heater portion, so that oxidation proceeds on the surface thereof.
  • the inert gas is circulating, the chamber is not completely sealed, so that oxidation also proceeds due to oxygen flowing into the chamber when the solder wire is supplied.
  • the temperature of the heater section in order to achieve good bonding, it is necessary to set the temperature of the heater section to a temperature about 30 ° C. to 70 ° C. higher than the melting point of the solder wire.
  • the temperature of the heater section when using a high melting point solder such as a Pb-based solder wire containing 5 mass% of Sn, the temperature of the heater section must be set to about 340 ° C to 380 ° C. The oxidation of the solder wire further proceeds.
  • the coated solder wire of the present invention is used instead of the conventional solder wire, it is possible to prevent oxidation during standby and melting by the action of the coating film.
  • the coated solder wire of the present invention is excellent in wet spreadability and bondability (bonding strength) even when the heater temperature (bonding temperature) is low or changes, and it can bond with very few voids. It can be easily and stably realized in industrial scale production. For this reason, the coated solder wire of the present invention can be suitably applied to the manufacture of a semiconductor element bonding substrate that requires high reliability and various devices using the substrate.
  • solder wire Zn, Ag, Sn, Pb, Cu, Au, In, Al, Ni, Sb, Ge, Te, and P having a purity of 99.9% or more were prepared as raw materials.
  • large flakes and bulk materials were cut or pulverized and adjusted to a size of 3 mm or less.
  • a predetermined amount was weighed from the raw material adjusted in this way and put into a graphite crucible.
  • the crucible was placed in a high-frequency melting furnace, and in order to suppress oxidation, the melting furnace was turned on in a state where 0.7 L / min or more of nitrogen per 1 kg of raw material was circulated.
  • the raw material was melted while sufficiently stirring with a mixing rod so as not to cause variation.
  • the melting furnace was turned off, the crucible was quickly taken out, and the obtained molten metal was cast into a solder mother alloy mold to obtain solder mother alloy ingots having different compositions.
  • the mold used was the same as a general mold used in the production of a solder mother alloy.
  • Each solder mother alloy ingot was processed into a wire shape using an extruder in an inert gas atmosphere. 1-30 solder wires (0.76 mm in diameter) were obtained.
  • the composition of these solder wires was measured using an ICP emission spectroscopic analyzer (manufactured by Shimadzu Corporation, ICPS-8100). The results are shown in Table 1.
  • Example 1 [Production of coated solder wire] Sample No. 1 is wound on the surface of the solder wire being transported by the method shown in FIG. 1 when winding the Pb-based solder wire with a solder wire automatic winder (manufactured by Tanabe Seisakusho Co., Ltd., TM type winding machine). A coating film made of a phosphorus-containing compound was formed using a pressure polymerization treatment apparatus (Plasma Polymer Lab System PAD-1 type, manufactured by Plasma Treat Co., Ltd.).
  • the length of each joint solder sample in the direction of the largest diameter in plan view of the joint solder is measured to be the maximum diameter X, and this maximum diameter X
  • the diameter in the direction orthogonal to the direction in which the film extends was measured as Y.
  • the height of the joining solder was measured and set as a height Z.
  • the aspect ratio determined for solder wire uncoated for A n and calculating the ratio of the aspect ratio A C covering the solder wire (A C / A n).
  • Examples 2 to 11, Comparative Examples 1 and 2 A coated solder wire was produced in the same manner as in Example 1 except that the coating material and the treatment conditions were changed as shown in Table 2, and the evaluations (a) to (d) were performed. The results are shown in Table 3.
  • the nozzle 8 is removed while conveying the solder wire 2 in the direction of arrow A.
  • the radicalized organophosphorus compound 5 was sprayed to form a coating film 3a (see FIG. 2 (a-1)).
  • the coating film 3b was formed in the same manner (see FIG. 2B-1).
  • the conveying jig 7 was further rotated by 120 ° so that the surface 7c became the bottom surface side, and the coating film 3c was formed in the same manner (see FIG. 2 (c-1)).
  • Comparative Example 4 Sample No. When winding 1 Pb-based solder wire with a solder wire automatic winder, it is immersed in a silicon-based coating agent (manufactured by Toray Dow Corning Co., Ltd., APZ6601) for 10 minutes and then dried at 120 ° C. for 10 minutes. A coated solder wire was prepared.
  • a silicon-based coating agent manufactured by Toray Dow Corning Co., Ltd., APZ6601
  • Example 6 A coated solder wire was produced in the same manner as in Example 1 except that the coating material was hexamethyldisiloxane and the processing conditions were changed as shown in Table 2, and the above (a) to (d) Evaluation was performed. The results are shown in Table 3.
  • Example 12 to 19 A coated solder wire was produced in the same manner as in Example 1 except that the Pb solder wire shown in Table 4 was used as the solder wire serving as the base material, and the evaluations (a) to (d) were performed. . The results are shown in Tables 4 and 5.
  • Example 20 to 28 A coated solder wire was produced in the same manner as in Example 1 except that the Sn-based solder wire shown in Table 4 was used as the solder wire serving as the base material, and the evaluations (a) to (d) were performed. . The results are shown in Tables 4 and 5.
  • Example 29 to 40 A coated solder wire was prepared in the same manner as in Example 1 except that the Zn-based solder wire shown in Table 4 was used as the solder wire serving as the base material, and the evaluations (a) to (d) were performed. . The results are shown in Tables 4 and 5.
  • the coated solder wires of Examples 1 to 40 had a thickness in the range of 1 nm to 100 nm, consisted of a coated film mainly containing a phosphorus-containing compound, and the coated film It was confirmed that there was little variation in film thickness. In particular, when the results of the coated solder wire of Example 1 and the coated solder wire of Comparative Example 3 were compared, it was confirmed that the coating uniformity of the coated solder wire of the present invention was dramatically improved.
  • the coated solder wires of Examples 1 to 40 had almost no change in the surface state before and after the neutral salt spray test, and compared with any of Comparative Examples 8 to 36 that were not coated, oxidation resistance It was confirmed to be excellent. Furthermore, in the joining solder obtained by die bonding using the coated solder wires of Examples 1 to 40, although the joining temperature was as low as 340 ° C., the coated solder wires of Comparative Examples 8 to 36 were not coated. Compared to any of these, it was confirmed that all the evaluations of the wet spreading property, the bonding property, and the heat cycle were good.
  • Example 1 the processing time in Example 1 was 1/3 or less of the processing time in Comparative Example 3. Therefore, according to the manufacturing method of the present invention, it was confirmed that the productivity of the coated solder wire is greatly improved. Therefore, the advantageous effects of the present invention are clear from the results of the above embodiments.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Die Bonding (AREA)

Abstract

L'invention concerne un fil de soudure revêtu fabriqué à échelle industrielle, ledit fil de soudure revêtu étant doté d'un film de revêtement dense qui est formé de manière uniforme, par une seule opération, sur toute la surface du fil de soudure, étant ainsi protégé d'une oxydation de surface pendant un stockage prolongé et lors de la fusion et ayant une excellente propriété d'étalement humide et une excellente propriété de joint. Le film de revêtement est formé par : mélange d'un gaz réactif, converti en un plasma à pression atmosphérique, avec un composé organophosphoré, qui est introduit par le biais d'un gaz porteur, afin de radicaliser le composé organophosphoré ; formation d'une zone de réaction qui est démarquée par un écoulement gazeux en spirale et dans laquelle le composé organophosphoré radicalisé est dispersé de façon uniforme ; et réaction du composé organophosphoré radicalisé avec un métal sur la surface du fil de soudure au sein de la zone de réaction, afin de former ainsi un film de revêtement, qui a une épaisseur de 1 à 100 nm et comprend un composé contenant du phosphore comme constituant principal, sur la surface du fil de soudure.
PCT/JP2016/070135 2015-07-27 2016-07-07 Fil de soudure revêtu et son procédé de fabrication WO2017018155A1 (fr)

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CN201680040706.8A CN107848076A (zh) 2015-07-27 2016-07-07 包覆焊料线及其制造方法
EP16830260.2A EP3330039A4 (fr) 2015-07-27 2016-07-07 Fil de soudure revêtu et son procédé de fabrication

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Publication number Priority date Publication date Assignee Title
EP3235586A4 (fr) * 2014-12-19 2018-07-18 Sumitomo Metal Mining Co., Ltd. Fil de soudure revêtu et son procédé de fabrication
WO2018232351A1 (fr) * 2017-06-16 2018-12-20 The Board Of Regents Of The University Of Nebraska Systèmes et procédés pour filtre électrique comprenant une structure en béton conductrice

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JP2004339583A (ja) * 2003-05-16 2004-12-02 Sony Corp 錫又は錫合金材の表面処理剤、錫又は錫合金材及びその表面処理方法、錫合金系はんだ材料及びこれを用いたはんだペースト、錫合金系はんだ材料の製造方法、電子部品、プリント配線板、並びに電子部品の実装構造
JP2006255762A (ja) * 2005-03-18 2006-09-28 Uchihashi Estec Co Ltd 電子部品用線状はんだ
JP2009515703A (ja) * 2005-11-10 2009-04-16 ウルヴァリン チューブ，インク． フラックスを含むエラストマーの長い連続層を持つろう付け結合材
JP2013123741A (ja) * 2011-12-15 2013-06-24 Sumitomo Metal Mining Co Ltd 塑性変形性に優れたＰｂフリーはんだ合金
JP2014195831A (ja) * 2013-03-08 2014-10-16 住友金属鉱山株式会社 被覆はんだ材料およびその製造方法
WO2016098836A1 (fr) * 2014-12-19 2016-06-23 住友金属鉱山株式会社 Fil de soudure revêtu et son procédé de fabrication

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JPH10166177A (ja) * 1996-12-10 1998-06-23 Tanaka Denshi Kogyo Kk 被覆半田材料及びその製造方法
JP2004339583A (ja) * 2003-05-16 2004-12-02 Sony Corp 錫又は錫合金材の表面処理剤、錫又は錫合金材及びその表面処理方法、錫合金系はんだ材料及びこれを用いたはんだペースト、錫合金系はんだ材料の製造方法、電子部品、プリント配線板、並びに電子部品の実装構造
JP2006255762A (ja) * 2005-03-18 2006-09-28 Uchihashi Estec Co Ltd 電子部品用線状はんだ
JP2009515703A (ja) * 2005-11-10 2009-04-16 ウルヴァリン チューブ，インク． フラックスを含むエラストマーの長い連続層を持つろう付け結合材
JP2013123741A (ja) * 2011-12-15 2013-06-24 Sumitomo Metal Mining Co Ltd 塑性変形性に優れたＰｂフリーはんだ合金
JP2014195831A (ja) * 2013-03-08 2014-10-16 住友金属鉱山株式会社 被覆はんだ材料およびその製造方法
WO2016098836A1 (fr) * 2014-12-19 2016-06-23 住友金属鉱山株式会社 Fil de soudure revêtu et son procédé de fabrication

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3235586A4 (fr) * 2014-12-19 2018-07-18 Sumitomo Metal Mining Co., Ltd. Fil de soudure revêtu et son procédé de fabrication
WO2018232351A1 (fr) * 2017-06-16 2018-12-20 The Board Of Regents Of The University Of Nebraska Systèmes et procédés pour filtre électrique comprenant une structure en béton conductrice

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