WO2011158668A1 - Bi-Al-Zn系Pbフリーはんだ合金 - Google Patents
Bi-Al-Zn系Pbフリーはんだ合金 Download PDFInfo
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- WO2011158668A1 WO2011158668A1 PCT/JP2011/062792 JP2011062792W WO2011158668A1 WO 2011158668 A1 WO2011158668 A1 WO 2011158668A1 JP 2011062792 W JP2011062792 W JP 2011062792W WO 2011158668 A1 WO2011158668 A1 WO 2011158668A1
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- mass
- solder
- alloy
- solder alloy
- temperature
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- 229910000679 solder Inorganic materials 0.000 title claims abstract description 126
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 97
- 239000000956 alloy Substances 0.000 title claims abstract description 97
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000000758 substrate Substances 0.000 abstract description 25
- 238000007711 solidification Methods 0.000 abstract description 23
- 230000008023 solidification Effects 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000009792 diffusion process Methods 0.000 abstract description 10
- 230000035882 stress Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 230000000694 effects Effects 0.000 description 17
- 229910052797 bismuth Inorganic materials 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 230000008018 melting Effects 0.000 description 14
- 238000002844 melting Methods 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 12
- 239000007790 solid phase Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 8
- 229910018137 Al-Zn Inorganic materials 0.000 description 7
- 229910018573 Al—Zn Inorganic materials 0.000 description 7
- 230000007547 defect Effects 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000005304 joining Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910016331 Bi—Ag Inorganic materials 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910018131 Al-Mn Inorganic materials 0.000 description 2
- 229910018461 Al—Mn Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000005219 brazing Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006023 eutectic alloy Substances 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910020830 Sn-Bi Inorganic materials 0.000 description 1
- 229910018728 Sn—Bi Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- 150000002843 nonmetals Chemical class 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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
- 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
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C23/00—Extruding metal; Impact extrusion
- B21C23/02—Making uncoated products
- B21C23/04—Making uncoated products by direct extrusion
- B21C23/08—Making wire, bars, tubes
-
- 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
- B23K35/0227—Rods, wires
-
- 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
- B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
- B23K35/0261—Rods, electrodes, wires
-
- 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
- C22C12/00—Alloys based on antimony or bismuth
-
- 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
Definitions
- the present invention relates to a Pb-free solder alloy, and more particularly to a Bi—Al—Zn-based Pb-free solder alloy.
- Solders used when bonding electronic components to a substrate are broadly classified into high temperature (about 260 ° C. to 400 ° C.) and medium to low temperature (about 140 ° C. to 230 ° C.) depending on the limit temperature of use.
- the medium / low temperature solder is composed mainly of Sn and Pb-free is put into practical use.
- Sn is a main component
- Ag is 1.0 to 4.0 mass%
- Cu is 2.0 mass% or less
- Ni is 0.5 mass% or less
- P is 0.2 mass%.
- Patent Document 2 describes a Pb-free solder having an alloy composition containing 0.5 to 3.5% by mass of Ag, 0.5 to 2.0% by mass of Cu, and the balance being Sn.
- Patent Document 3 discloses a Bi / Ag brazing material containing 30 to 80% by mass of Bi and having a melting temperature of 350 to 500 ° C.
- Patent Document 4 discloses a solder alloy in which a binary eutectic alloy is added to a eutectic alloy containing Bi and an additional element is further added. This solder alloy is a quaternary or higher multi-component solder. However, it has been shown that the liquidus temperature can be adjusted and variations can be reduced.
- Patent Document 5 discloses a solder alloy in which Cu—Al—Mn, Cu, or Ni is added to Bi. These solder alloys include a power semiconductor element and an insulator substrate having a Cu layer on the surface. It is described that, when used in the above, it is difficult to form an unnecessary reaction product at the joint interface with the solder, so that occurrence of defects such as cracks can be suppressed.
- Patent Document 6 among 100% by mass of the solder composition, a first metal element composed of 94.5% by mass or more of Bi, a second metal element composed of 2.5% by mass of Ag, and Sn: 0.1 to 0.5 mass%, Cu: 0.1 to 0.3 mass%, In: 0.1 to 0.5 mass%, Sb: 0.1 to 3.0 mass%, and Zn: 0
- a solder composition comprising a third metal element containing 0.1 to 3.0% by mass in total of at least one selected from the group consisting of 0.1 to 3.0% by mass is shown.
- Patent Document 7 discloses a Pb-free solder composition containing 0.3 to 0.5% by mass of Ni in a Bi-based alloy containing at least one of Ag, Cu, Zn and Sb as an accessory component.
- the Pb-free solder has a solidus temperature of 250 ° C. or higher and a liquidus temperature of 300 ° C. or lower.
- Patent Document 8 discloses a binary alloy containing Bi, and it is described that this binary alloy has an effect of suppressing the occurrence of cracks in the soldering structure.
- the working temperature since materials having relatively low heat resistance such as thermoplastic resins and thermosetting resins are generally used for electronic parts and substrates, the working temperature must be less than 400 ° C., preferably 370 ° C. or less. There is. However, for example, in the Bi / Ag brazing material disclosed in Patent Document 3, since the liquidus temperature is as high as 400 to 700 ° C., it is estimated that the working temperature at the time of joining is also 400 to 700 ° C. or higher. It will exceed the heat resistance temperature of electronic parts and substrates.
- the main component of the solder alloy is Bi
- Ni layer when a Ni layer is formed on the surface of the electronic component in order to improve the bondability with the solder alloy, the Ni layer reacts rapidly with Bi contained in the solder alloy, and Ni and Bi In addition to forming a brittle alloy, the Ni layer may be broken or peeled and diffused into Bi, thereby significantly reducing the bonding strength.
- a layer of Ag, Au, or the like may be provided on the Ni layer. In this case, Ag or Au is intended to prevent oxidation of the Ni layer and improve wettability, so it quickly diffuses into the solder alloy. Therefore, there is almost no effect of suppressing Ni diffusion.
- Patent Document 5 the case where the bonding surface with the solder alloy is not the Cu layer but the Ni layer is taken as a comparative example, and in the case of a solder alloy in which Cu—Al—Mn, Cu, or Ni is added to Bi, bonding is performed. It is described that a large amount of Bi 3 Ni is formed at the interface, and a large number of voids are observed around it. Further, it is described that this Bi 3 Ni has a very brittle property and it has been confirmed that it is difficult to obtain reliability with respect to a heat cycle test under severe conditions.
- Ni forms a brittle alloy with Bi as described above. That is, as can be seen from the Bi-Ni binary phase diagram, when a large amount of Bi is present, a brittle alloy called Bi 3 Ni alloy is formed. When Ni is contained in an amount of 0.3 to 0.5% by mass, a very brittle alloy phase is dispersed in the solder, and it is assumed that the originally brittle Bi-based solder is further embrittled.
- Patent Document 4 and Patent Document 8 do not mention anything about the problem of Ni diffusion into Bi and the preventive measures thereof.
- Patent Document 8 discloses Bi—Ag system, Bi—Cu system, Bi—Zn system, etc., but for Bi—Ag system, it is especially necessary to take measures against Ni diffusion. There is nothing to mention about.
- the Bi-Cu system the present inventors have confirmed that since the solid solution amount of Cu in Bi is very small, a Cu phase having a high melting point is precipitated, resulting in a problem in bonding properties. No countermeasures are described for this.
- the Bi—Zn system wettability is reduced due to highly reducible Zn, and it can be presumed that it is difficult to join electronic parts, etc., but this is not mentioned, and description of the reaction between Ni and Bi Nor.
- solder composition containing 2.5% by mass of Ag as disclosed in Patent Document 6 since Ag promotes the reaction between Bi and Ni, for example, Sn is 0.5% by mass or more, Even if Zn is contained in an amount of 3.0% by mass or more, the reaction between Bi and Ni and the diffusion of Ni into Bi cannot be suppressed, and this is a solder material that has low bonding strength and cannot withstand practical use. The inventor has confirmed by experiment.
- Patent Document 6 describes that in order to suppress damage to the substrate during soldering, it is effective to take measures to relieve stress generated during solder solidification, and therefore an alloy that does not shrink during solidification. The selection of the composition is also described. Further, examples of alloy compositions that do not shrink during solidification include Bi and Ga, which are metal elements that expand in volume during solidification. It is described that Bi was selected as the main component of the solder composition, and the Bi-2.5 wt% Ag solder composition was considered promising in consideration of the melting point, workability, and the like.
- the shrinkage rate at the time of solidification ( ⁇ means expansion, + means shrinkage) is such that Bi is ⁇ 3.2 to ⁇ 3.4% and Ag is + 6.4% to + 6.8%. If the amount of addition is 2.5% by mass, the rate of expansion due to Bi during solidification is still too much and residual stress is generated. Therefore, it is considered difficult to suppress damage to the substrate that may occur during soldering, and to obtain bondability and reliability that can withstand practicality.
- the reflow temperature of the high-temperature solder is generally set to about 260 ° C., but actually, a temperature higher than this temperature is often set according to individual manufacturing conditions. In a high reflow temperature region set in such a high-temperature solder, a solder material having a slightly higher solid phase temperature is required to withstand the reflow temperature.
- the solid phase temperature is 262 ° C., and if the third and subsequent elements are added to this alloy, the solid phase temperature further decreases.
- the solid phase temperature of the Bi—Zn alloy of Patent Document 8 is 254.5 ° C., and it is estimated that it is difficult to keep fixing the electronic component when the reflow temperature is close to 300 ° C.
- the present invention is a Bi-based solder that has low residual stress during solidification, high bonding strength and high reliability, and prevents Ni—Bi reaction and Ni diffusion when bonding Ni-containing electronic parts and substrates.
- An object of the present invention is to provide a Pb-free solder alloy that can be suppressed and that can withstand a high reflow temperature.
- the first Pb-free solder alloy of the present invention contains Al in an amount of 0.03 to 0.70% by mass and Zn in an amount of 0.2 to 14.0% by mass. And the balance is made of Bi except for inevitable impurities.
- the second Pb-free solder alloy of the present invention contains Al in a range of 0.03 mass% to 0.70 mass% and contains Zn in a range of 0.2 mass% to 14.0 mass%. It is characterized by not containing over 0.50% by mass and the balance being made of Bi except for inevitable impurities.
- the residual stress at the time of solidification is reduced, and high bonding strength and high reliability can be obtained. Further, it is possible to suppress the reaction between the Ni layer possessed by the electronic component or the like and Bi in the solder alloy and the diffusion of Ni into the Bi-based solder. Furthermore, a solder alloy that can substantially withstand a reflow temperature of 265 ° C. or higher can be realized.
- the composition of the first Pb-free solder alloy of the present invention is a ternary Pb-free solder alloy containing Bi as the first element, that is, the main component. Specifically, Al is contained in an amount of 0.03 to 0.70% by mass, Zn is contained in an amount of 0.2 to 14.0% by mass, and the balance is made of Bi except for inevitable impurities. . As described above, the first Pb-free solder alloy of the present invention does not contain elements other than Bi, Al and Zn except for impurities inevitably contained, and does not contain Sn in particular.
- a very characteristic phenomenon that occurs in Bi-Al-Zn-based Pb-free solder alloys containing Bi as a main component as described above is that when the molten solder alloy is cooled and solidified during the joining of electronic components, etc.
- the phenomenon of swelling can be mentioned. Residual stress is generated in the solder alloy, electronic parts, and the like due to the expansion during the solidification. It is clear that the bonding strength and durability are reduced by this residual stress.
- the first Pb-free solder alloy of the present invention Al that shrinks during solidification is added to the solder alloy. That is, in order to relieve the volume expansion of Bi during solidification, the expansion of Bi is softened by the shrinkage of Al by adding Al, and the volume change of the entire solder alloy is reduced. Thereby, the residual stress of the solder alloy is reduced.
- Al can be expected to have further important effects. That is, by adding Al, the solid phase temperature and liquid phase temperature of the solder alloy can be further increased. As can be seen from the Bi—Al binary phase diagram, the solid phase temperature of Bi—Al is 270 ° C., and the melting point of Bi (271 ° C.) is hardly lowered. Furthermore, the liquidus temperature can be increased by adding a small amount of Al, and Bi-based solder can be used at a higher temperature. Thus, by adding Al, it is possible to achieve both a reduction in residual stress and a high melting point, and it is also possible to improve wettability due to the strong reducibility of Al as will be described later.
- Zn further improves the characteristics of this Bi-Al alloy. That is, by adding Zn, an Al—Zn alloy is produced, which greatly improves the workability in the vicinity of the eutectic point. Furthermore, since Zn is highly reactive with Ni, it reacts with the Ni layer to form an alloy layer. This alloy layer also has an effect of suppressing the formation of a fragile phase caused by the reaction between Bi and Ni. Thus, Zn improves the workability together with Al, and further suppresses the reaction between Bi and Ni to suppress the formation of a brittle Bi-Ni phase, so these effects improve the bonding strength, reliability, etc. There is an effect to make.
- the second Pb-free solder alloy of the present invention contains 0.03 mass% to 0.70 mass% of Al, and contains 0.2 mass% to 14.0 mass% of Zn, and P is 0.500 mass%. %, And the balance is Bi except for inevitable impurities.
- This second Pb-free solder alloy contains Al and Zn in Bi as a main component at the same content as the first Pb-free solder alloy. Thereby, it can have the outstanding characteristic equivalent to a 1st Pb free solder alloy.
- the second Pb-free solder alloy may have higher wettability than the first Pb-free solder alloy by including P at a content of 0.500% by mass or less as necessary. it can. This is because by adding P in the range of the content of 0.500% by mass or less, even if Bi—Al—Zn solder alloy has insufficient wettability, P having a strong reducing property is effective. This is because high wettability is obtained.
- Bi is the first element, that is, the main component of the high-temperature Pb-free solder alloy of the present invention.
- Bi belongs to the Va group element (N, P, As, Sb, Bi), and its crystal structure is a trigonal crystal (rhombohedral crystal) with a low symmetry and a very brittle metal. It can be easily seen that the fracture surface is a brittle fracture surface.
- pure Bi is poor in ductile properties, and the experimental result shows that the elongation rate of Bi is less than 1.0%.
- Bi is a special metal that expands during solidification, and the shrinkage rate during solidification ( ⁇ means expansion and + means contraction) is ⁇ 3.2% to ⁇ 3.4%. Residual stress is generated by this expansion, and bonding strength and reliability are lowered.
- Bi also has a problem that it easily reacts with Ni to form a brittle alloy, resulting in a decrease in bondability and the like.
- Al is an essential additive element in the high-temperature Pb-free solder alloy of the present invention.
- the addition of Al makes it possible to reduce the residual stress associated with the expansion of Bi during solidification, and to realize a high liquidus temperature and a high solidus temperature. Furthermore, effects such as improved wettability can be obtained.
- the shrinkage rate during solidification of Bi is -3.2% to -3.4% as described above, while the shrinkage rate during solidification of Al is +6.4 to +6. 8%. Therefore, the expansion due to Bi can be alleviated to some extent.
- the liquidus temperature becomes too high and good bonding cannot be obtained, so the content of Al in the solder alloy is limited.
- Al has an excellent melting point adjusting effect, and Al also plays an important role in this respect. That is, even when Al is added, the solid phase temperature can be maintained at 270 ° C. with almost no decrease, and the liquid phase temperature can be easily increased by adjusting the Al content. As a result, the reflow temperature that can be tolerated can be increased or adjusted to a more desirable temperature. Furthermore, due to the strong reducibility of Al, Al itself oxidizes at the time of joining with an electronic component, and has the effect of significantly improving the wettability of the solder.
- an appropriate amount of Al is added in consideration of characteristics such as relaxation of residual stress, adjustment of melting point, and wettability. Specifically, it is added so that Al is contained in the solder alloy in an amount of 0.03 mass% or more and 0.70 mass% or less. If this amount is less than 0.03 mass%, the expected effect is difficult to obtain because of too little. On the other hand, if it is added in an amount of more than 0.70% by mass, Al having a high melting point is segregated, resulting in problems such as deterioration of the bondability.
- Zn is an essential additive element similar to Bi and Al in the high-temperature Pb-free solder alloy of the present invention.
- Zn is added to the Bi—Al alloy.
- an Al—Zn alloy is produced.
- the crystal becomes finer and the workability is remarkably improved.
- the upper limit of the content of Al in the solder alloy is 0.70% by mass, so the effect of adding Zn is great when improving workability.
- Zn is highly reactive with Ni, it reacts with the Ni layer to form an alloy layer. This plays an important role of suppressing the formation of a brittle phase due to the reaction between Bi and Ni, and further suppressing the diffusion of Ni into Bi. As a result, joint strength and reliability are dramatically improved. Thus, Zn has the effect of improving workability and suppressing the reaction between Bi and Ni and improving the bonding strength, reliability, and the like.
- the optimum content of Zn that exhibits such excellent effects depends on the bonding area of the electronic component, the thickness of the solder, the thickness of the Ni layer, the reflow temperature, the reflow time, etc., but is generally 0.2% by mass. Above 14.0 mass%. If this amount is less than 0.2% by mass, the content is too small to be added. On the other hand, if it exceeds 14.0% by mass, the solid phase temperature of Bi—Zn is 254 ° C., so there is a high possibility that the proportion of the liquid phase at the time of reflow increases so that the electronic component cannot be fixed. .
- P is an element added as necessary, and by adding P, the wettability and bondability of the Bi—Al—Zn alloy can be further improved.
- the reason why the effect of improving wettability is increased by the addition of P is that P is highly reducible and suppresses oxidation of the solder alloy surface by oxidizing itself.
- P has an effect of further reducing the generation of voids during bonding. That is, as described above, since P easily oxidizes itself, oxidation proceeds preferentially over Bi, which is the main component of solder, during bonding. As a result, it is possible to prevent the solder mother phase from being oxidized and to ensure wettability. As a result, good bonding is possible, and voids are hardly generated.
- P is very reducible, so that the effect of improving wettability is exhibited even when a small amount is added. On the contrary, even if it is added in a certain amount or more, the effect of improving the wettability does not change. If it is excessively added, P oxide may be generated on the solder surface, or P may form a brittle phase and become brittle. Therefore, the addition of P is preferably a trace amount.
- the upper limit of the content of P in the solder alloy is 0.500% by mass.
- P exceeds this upper limit, the oxide covers the solder surface, and conversely, wettability may be reduced.
- P has a very small amount of solid solution in Bi, if the content is large, brittle P oxide is segregated, and the reliability is lowered. It has been confirmed that wire breakage is likely to occur, especially when processing wires and the like.
- One of the major objects of the present invention is to withstand a reflow temperature as high as possible by increasing the solid phase temperature as much as possible in a Bi-based solder.
- Sn is added, although there are various merits such as an effect of suppressing Ni diffusion, there is a problem that the solid phase temperature is greatly lowered.
- the solid phase temperature of the Sn—Bi alloy is very low at 139 ° C., and if it is contained by several mass% of the content in the solder alloy, a liquid phase is reliably generated at the time of reflow and the electronic component is kept fixed. Is considered difficult. Therefore, the Pb-free solder alloy of the present invention does not contain Sn.
- the Pb-free solder alloy for high temperature of the present invention described above is used for joining an electronic component and a substrate, it is durable even when used under severe conditions such as an environment where heat cycles are repeated.
- a highly reliable and reliable electronic substrate can be provided. Therefore, by mounting this electronic board on, for example, power semiconductor devices such as thyristors and inverters, various control devices mounted on automobiles, devices used under harsh conditions such as solar cells, these various devices Can be further improved in reliability.
- the crucible containing the raw material was put into a high-frequency melting furnace, and nitrogen was flowed at a flow rate of 0.7 L / min or more per 1 kg of the raw material in order to suppress oxidation.
- the melting furnace was turned on to heat and melt the raw material.
- the metal began to melt, it was stirred well with a mixing rod and mixed uniformly so as not to cause local compositional variations.
- the high-frequency power supply was turned off, and the molten metal in the crucible was quickly taken out and poured into the mold of the solder mother alloy.
- a mold having the same shape as that generally used in the manufacture of solder alloys was used.
- solder mother alloys of Samples 1 to 13 were produced by changing the mixing ratio of each raw material.
- the compositions of the solder mother alloys of Samples 1 to 13 were analyzed using an ICP emission spectroscopic analyzer (SHIMAZU S-8100). The analysis results are shown in Table 1 below.
- each of the solder mother alloys of Samples 1 to 13 shown in Table 1 was subjected to the following wire workability evaluation, wettability (bondability) evaluation, heat cycle test, and atmospheric heat resistance test. It was.
- evaluation of solder wettability or the like does not usually depend on the shape of the solder, evaluation may be performed using a shape such as a wire, a ball, or a paste. However, in this example, the evaluation was performed by forming the wire.
- the wettability (joinability) evaluation was performed using the wire-shaped solder alloy obtained in the evaluation of the wire workability.
- a wettability tester device name: atmosphere control type wettability tester
- nitrogen was flowed from four locations around the heater part (nitrogen flow rate: each 12 L / min).
- the heater set temperature was set to 340 ° C. and heated.
- a Cu substrate (plate thickness: about 0.1 ⁇ m) on which an Ni plating layer (film thickness: 4.0 ⁇ m) and an upper Ag vapor deposition layer (film thickness: 0.15 ⁇ m) were formed. 70 mm) was set in the heater section and heated for 25 seconds. Next, the solder alloy was placed on the Cu substrate and heated for 25 seconds. After the heating was completed, the Cu substrate was picked up from the heater part and once moved to a place where the nitrogen atmosphere next to the Cu substrate was maintained and cooled. After sufficiently cooling, it was taken out into the atmosphere and a joint portion was confirmed.
- ⁇ Heat cycle test> A heat cycle test was conducted to evaluate the reliability of solder joints. This test was performed using a Cu substrate to which a solder alloy obtained in the same manner as the wettability evaluation was bonded. First, with respect to the Cu substrate to which the solder alloy was bonded, cooling at ⁇ 40 ° C. and heating at 150 ° C. were taken as one cycle, and this was repeated for a predetermined cycle. Thereafter, the Cu substrate to which the solder alloy was bonded was embedded in the resin, the cross-section was polished, and the bonded surface was observed by SEM (device name: HITACHI S-4800). The case where the joint surface was peeled off or the solder was cracked was indicated as “X”, and the case where there was no such defect and the same joint surface as in the initial state was maintained as “ ⁇ ”.
- the solder mother alloys of Samples 1 to 9 that satisfy the requirements of the present invention show good characteristics in each evaluation item. In other words, even if it was processed into a wire, it could be wound up automatically without being cut and showed good workability. Also, the wettability to the surface on which Ag was deposited was very good. In particular, the sample to which P was added spreads very quickly, and the sample spread thinly when the sample contacted the Cu substrate. Good results were also obtained in the heat cycle test and the heat resistance test in the atmosphere, which are tests related to reliability. In the heat cycle test, no defect appeared even after 500 cycles. In the air heat test, even after 1000 hours had passed. No defect appeared.
- the solder mother alloys of Comparative Samples 10 to 13 that did not satisfy the requirements of the present invention had undesirable results in at least any of the characteristics.
- the wire is broken at least once when processed into a wire, and the wettability to the surface on which Ag is vapor-deposited is often poor.
- defects occur in all samples up to 300 times, and the atmosphere In the middle heat resistance test, defects occurred in all samples after 1000 hours.
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Abstract
Description
Biは本発明の高温用Pbフリーはんだ合金の第1元素、すなわち主成分をなしている。BiはVa族元素(N、P、As、Sb、Bi)に属し、その結晶構造は、対称性の低い三方晶(菱面体晶)で非常に脆い金属であり、引張試験などを行うとその破面は脆性破面であることが容易に見て取れる。つまり純Biは延性的な性質に乏しく、実験結果ではBiの伸び率は、1.0%未満であった。また、Biは凝固時に膨張する特殊な金属であり、この凝固時の収縮率(-が膨張、+が収縮を意味する)は-3.2%~-3.4%である。この膨張により残留応力が発生し、接合強度や信頼性が低下する。また、BiはNiと容易に反応し、脆い合金を生成し、接合性等が低下してしまうという問題も持っている。
Alは本発明の高温用Pbフリーはんだ合金において、必須の添加元素である。Alの添加によりBiの凝固時の膨張に伴う残留応力の低減が可能となる上、高い液相温度および高い固相温度の実現が可能となる。さらには濡れ性の向上などの効果も得られる。具体的に説明すると、Biの凝固時の収縮率は前述したように-3.2%~-3.4%であるのに対して、Alの凝固時の収縮率は+6.4~+6.8%である。よって、Biによる膨張をある程度緩和することができる。ただし、Alを多量に添加すると、液相温度が高くなりすぎて良好な接合が得られなくなるため、はんだ合金中のAlの含有量は制限を受ける。
Znは本発明の高温用Pbフリーはんだ合金において、BiおよびAlと同様に必須の添加元素である。Bi-Al合金にZnを添加することにより、Al-Zn合金が生成され、とくにAl-Zn合金の共晶組成付近では結晶が微細化して加工性が格段に向上する。前述したように、はんだ合金中のAlの含有量は上限で0.70質量%とあまり多くないため、加工性を向上させたい場合には、Znの添加効果は大きい。
Pは必要に応じて添加される元素であり、Pを添加することによって、Bi-Al-Zn合金の濡れ性および接合性をさらに向上させることができる。Pの添加により濡れ性向上の効果が大きくなる理由は、Pは還元性が強く、自ら酸化することによりはんだ合金表面の酸化を抑制することによる。
次にSnについて述べる。本発明は、Bi系はんだにおいて固相温度を可能な限り上げることにより、出来るだけ高いリフロー温度に耐えることを大きな目的の一つとしている。Snを添加した場合、Ni拡散抑制効果等、様々なメリットがあるものの、固相温度を大きく下げてしまうという問題がある。つまり、Sn-Bi合金の固相温度は139℃と非常に低く、はんだ合金中の含有量によるものの数質量%含まれる場合はリフロー時に確実に液相が生成され、電子部品を固定し続けることは困難と考えられる。よって、本発明のPbフリーはんだ合金ではSnを含まないものとする。
上記表1に示す試料1~13のはんだ母合金を各々押出機にセットし、外径0.80mmのワイヤを加工した。具体的には、あらかじめ押出機をはんだ組成に適した温度に加熱しておき、各はんだ母合金をセットした。押出機出口から押し出されるワイヤ状のはんだは、まだ熱く酸化が進行し易いため、押出機出口は密閉構造とし、その内部に不活性ガスを流した。これにより、可能な限り酸素濃度を下げて酸化が進まないようにした。油圧で圧力を上げていき、はんだ母合金をワイヤ形状に押し出していった。ワイヤの押出速度はワイヤが切れたり変形したりしないように予め調整しておいた速度とし、同時に自動巻取機を用いて同じ速度で巻き取るようにした。
濡れ性(接合性)評価は、上記ワイヤ加工性の評価の際に得たワイヤ状のはんだ合金を用いて行った。まず、濡れ性試験機(装置名:雰囲気制御式濡れ性試験機)を起動し、加熱するヒーター部分に2重のカバーをしてヒーター部の周囲4箇所から窒素を流した(窒素流量:各12L/分)。その後、ヒーター設定温度を340℃にして加熱した。
はんだ接合の信頼性を評価するためにヒートサイクル試験を行った。なお、この試験は、上記濡れ性評価と同様にして得たはんだ合金が接合されたCu基板を用いて行った。まず、はんだ合金が接合されたCu基板に対して、-40℃の冷却と150℃の加熱を1サイクルとして、これを所定のサイクル繰り返した。その後、はんだ合金が接合されたCu基板を樹脂に埋め込み、断面研磨を行い、SEM(装置名:HITACHI S-4800)により接合面の観察を行った。接合面に剥がれやはんだにクラックが入っていた場合を「×」、そのような不良がなく、初期状態と同様の接合面を保っていた場合を「○」とした。
はんだ接合の信頼性を評価するために大気中耐熱試験を行った。なお、この試験は、ヒートサイクル試験で用いた試料と同様のはんだ合金が接合されたCu基板を用いて行った。まず、150℃に加熱したオーブンに試料を入れ、1000時間経過後、取り出した。その後、はんだ合金が接合されたCu基板を樹脂に埋め込み、断面研磨を行い、SEM(装置名:HITACHI S-4800)により接合面の観察を行った。接合面に剥がれやはんだにクラックが入っていた場合を「×」、そのような不良がなく、初期状態と同様の接合面を保っていた場合を「○」とした。上記説明した評価および試験の結果を表2に示す。
Claims (2)
- Alを0.03質量%以上0.70質量%以下含有すると共にZnを0.2質量%以上14.0質量%以下含有し、残部が不可避不純物を除いてBiからなることを特徴とするPbフリーはんだ合金。
- Alを0.03質量%以上0.70質量%以下含有すると共にZnを0.2質量%以上14.0質量%以下含有し、Pは0.500質量%を超えて含有しておらず、残部が不可避不純物を除いてBiからなることを特徴とするPbフリーはんだ合金。
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CN2011800299535A CN103068518A (zh) | 2010-06-16 | 2011-06-03 | Bi-Al-Zn系无铅焊料合金 |
GB1300359.5A GB2494831B (en) | 2010-06-16 | 2011-06-03 | Bi-Al-Zn-based Pb-free solder alloy |
JP2012520369A JP5212573B2 (ja) | 2010-06-16 | 2011-06-03 | Bi−Al−Zn系Pbフリーはんだ合金 |
DE112011102028.7T DE112011102028B4 (de) | 2010-06-16 | 2011-06-03 | Bi-Al-Zn-basierte Pb-freie Lotlegierung |
US13/702,407 US9211614B2 (en) | 2010-06-16 | 2011-06-03 | Bi—Al—Zn—based Pb-free solder alloy |
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JP2013146765A (ja) * | 2012-01-20 | 2013-08-01 | Sumitomo Metal Mining Co Ltd | Mgを含有するPbフリーBi系はんだ合金 |
CN114227059A (zh) * | 2022-01-06 | 2022-03-25 | 南京工程学院 | Bi@MAX核壳结构、高可靠无铅焊料及其制备方法 |
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JP4807465B1 (ja) * | 2010-06-28 | 2011-11-02 | 住友金属鉱山株式会社 | Pbフリーはんだ合金 |
US9590155B2 (en) * | 2012-06-06 | 2017-03-07 | Cree, Inc. | Light emitting devices and substrates with improved plating |
CN107275431A (zh) * | 2017-05-08 | 2017-10-20 | 江苏东昇光伏科技有限公司 | 一种太阳能光伏电池用焊带及其制备方法 |
CN114905183B (zh) * | 2022-05-11 | 2024-04-09 | 湘潭大学 | 一种Bi-Ag-Zn系无铅焊料及其制备方法和应用 |
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JP2001353590A (ja) * | 2000-06-12 | 2001-12-25 | Murata Mfg Co Ltd | はんだ組成物およびはんだ付け物品 |
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CN114227059A (zh) * | 2022-01-06 | 2022-03-25 | 南京工程学院 | Bi@MAX核壳结构、高可靠无铅焊料及其制备方法 |
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TWI442987B (zh) | 2014-07-01 |
CN103068518A (zh) | 2013-04-24 |
TW201204502A (en) | 2012-02-01 |
GB2494831B (en) | 2014-03-12 |
JP5212573B2 (ja) | 2013-06-19 |
US9211614B2 (en) | 2015-12-15 |
GB2494831A (en) | 2013-03-20 |
DE112011102028T5 (de) | 2013-04-18 |
JPWO2011158668A1 (ja) | 2013-08-19 |
GB201300359D0 (en) | 2013-02-20 |
DE112011102028B4 (de) | 2017-02-09 |
US20130078138A1 (en) | 2013-03-28 |
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