WO2022107806A1 - はんだ合金、はんだボール、及びはんだ継手 - Google Patents

はんだ合金、はんだボール、及びはんだ継手 Download PDF

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Publication number
WO2022107806A1
WO2022107806A1 PCT/JP2021/042233 JP2021042233W WO2022107806A1 WO 2022107806 A1 WO2022107806 A1 WO 2022107806A1 JP 2021042233 W JP2021042233 W JP 2021042233W WO 2022107806 A1 WO2022107806 A1 WO 2022107806A1
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WIPO (PCT)
Prior art keywords
mass
solder
solder alloy
alloy
free
Prior art date
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PCT/JP2021/042233
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English (en)
French (fr)
Japanese (ja)
Inventor
裕貴 飯島
俊策 吉川
寛大 出井
貴大 松藤
昂太 杉澤
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Senju Metal Industry Co Ltd
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Senju Metal Industry Co Ltd
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Filing date
Publication date
Priority to MX2023005700A priority Critical patent/MX2023005700A/es
Priority to CA3198256A priority patent/CA3198256C/en
Priority to JP2022517181A priority patent/JP7100283B1/ja
Priority to MYPI2023001946A priority patent/MY199315A/en
Priority to EP24196170.5A priority patent/EP4578592A1/en
Priority to KR1020257041766A priority patent/KR20260004560A/ko
Priority to KR1020237016199A priority patent/KR102901735B1/ko
Priority to US18/033,750 priority patent/US12583060B2/en
Application filed by Senju Metal Industry Co Ltd filed Critical Senju Metal Industry Co Ltd
Priority to EP21894680.4A priority patent/EP4249165A4/en
Priority to CN202180077121.4A priority patent/CN116472140A/zh
Publication of WO2022107806A1 publication Critical patent/WO2022107806A1/ja
Priority to JP2022097574A priority patent/JP7144708B2/ja
Priority to JP2022097573A priority patent/JP2022130498A/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/26Selection of soldering or welding materials proper with the principal constituent melting at less than 400°C
    • B23K35/262Sn as the principal constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering or brazing
    • B23K35/0244Powders, particles or spheres; Preforms made therefrom
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C13/00Alloys based on tin
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C13/00Alloys based on tin
    • C22C13/02Alloys based on tin with antimony or bismuth as the next major constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2101/00Articles made by soldering, welding or cutting
    • B23K2101/36Electric or electronic devices
    • B23K2101/40Semiconductor devices
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/30Assembling printed circuits with electric components, e.g. with resistors
    • H05K3/32Assembling printed circuits with electric components, e.g. with resistors electrically connecting electric components or wires to printed circuits
    • H05K3/34Assembling printed circuits with electric components, e.g. with resistors electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/346Solder materials or compositions specially adapted therefor

Definitions

  • the present invention relates to lead-free and antimony-free solder alloys, solder balls, and solder joints. This application claims priority based on US Patent Application No. 63 / 115,611, which was provisionally filed in the United States on November 19, 2020, the contents of which are incorporated herein by reference.
  • a semiconductor package such as QFP (Quad Flat Package) is used, and high integration and high functionality are achieved at the semiconductor chip level.
  • QFP Quad Flat Package
  • a packaging process is adopted in which a silicon chip cut out from a silicon wafer is die-bonded to a lead frame.
  • a silicon chip and a lead frame are die-bonded with a solder alloy to form a solder joint.
  • solder bumps are formed using solder balls.
  • an adhesive flux is applied to the microelectrode, and the solder ball is placed on the electrode to which the flux is applied. After that, it is heated in a reflow furnace to melt the solder balls, and the molten solder gets wet with the microelectrodes, so that solder bumps are formed on the microelectrodes.
  • Sn—Ag—Cu solder alloys are widely used, and are used not only in the form of solder balls but also for die bonding.
  • this solder alloy it may be necessary to improve heat cycle resistance, impact resistance, and discoloration resistance in various recent demands. Therefore, various studies have been made on Sn—Ag—Cu solder alloys, which have been widely used in the past, in order to improve these characteristics.
  • Patent Document 1 discloses a solder alloy containing Ni and Ge as optional elements in the Sn—Ag—Cu solder alloy. It is disclosed that this solder alloy exhibits heat cycle resistance when it contains Ni, and exhibits impact resistance and discoloration resistance when it contains Ge.
  • solder alloy Sn-Ag-Cu-Ni-Ge solder alloy
  • Patent Document 1 simultaneously exhibits three effects of impact resistance, discoloration resistance, and heat cycle resistance. It is an excellent alloy that can be used. However, there is room for further improvement in alloy design.
  • solder alloy has a unique addition significance for each element, it is an integral combination of all the constituent elements, and since each constituent element influences each other, the constituent elements are contained in a well-balanced manner as a whole. Need to be.
  • the content of each constituent element is individually optimized, which is sufficient to obtain the effect described in Patent Document 1 at the time of filing of Patent Document 1. It is probable that the alloy composition was different.
  • the content of each constituent element is individually optimized, and then the constituent elements as a whole are used. It is necessary to contain it in a well-balanced manner.
  • an object of the present invention is to provide a lead-free and antimony-free solder alloy, a solder ball, and a solder joint having a melting point of about 230 ° C. and a tensile strength of 50 MPa or more.
  • the solder alloy is composed of two or more kinds of elements, and the effect of each of them may affect the characteristics of the entire solder alloy. However, as mentioned above, all the constituent elements are integrated into each other. The constituent elements are interrelated. The present inventors have focused on designing an alloy having an improved share strength so that the same constituent elements as the solder alloy described in Patent Document 1 can be applied not only to BGA but also to QFP.
  • a silicon chip and a lead frame are die-bonded with a solder alloy to form a solder joint.
  • a back metal having a Ni layer on the outermost layer is formed on the silicon chip, for example, in order to improve the wettability with the solder and improve the adhesion strength.
  • a barrier layer such as Ti is usually formed on the back metal in order to prevent Ni from diffusing into the silicon chip.
  • the wettability of the solder alloy to Ti is very poor, and the back metal wets and repels the molten solder. Further, even if a small amount of Ni layer remains, Ni atoms diffuse into the molten solder, while Ti hardly diffuses into Ni. For this reason, voids increase at the atomic level at the interface between the Ti layer and the Ni layer, which are barrier layers, and the adhesive strength at the interface between the remaining Ni layer and the Ti layer is extremely lowered. As a result, the joint portion after die bonding may be inferior in impact resistance and heat cycle resistance. As described above, it is extremely important for die bonding to leave the Ni layer of the back metal.
  • the inventors reexamined the significance of adding each constituent element, and then conducted a detailed composition search in consideration of the balance of each constituent element.
  • the inventors have found that when the Ag, Cu, Bi and Ni contents are appropriate, the difference between the liquidus temperature and the solidus temperature of the solder alloy (hereinafter, this may be referred to as ⁇ T). Was found to be in an appropriate range.
  • the inventors have also studied the miniaturization of intermetallic compounds formed at the bonding interface in order to improve the bonding strength of the solder joint. Since a compound of Cu and Sn is formed at the bonding interface, it is necessary that the content ratio of Cu and Sn is in a predetermined range. Further, in the compound of Cu and Sn, attention was paid to the fact that the compound can be miniaturized by substituting a part of Cu with Ni. Furthermore, since the liquidus temperature of the solder alloy fluctuates greatly depending on the content of Cu and Ni, studies were conducted to control the viscosity at the time of melting by preventing the ⁇ T from becoming too large and to suppress the growth of the Sn compound. Was done.
  • the inventors adjust the Ag content to a predetermined range to suppress the precipitation of coarse Ag 3 Sn and to precipitate fine Ag 3 Sn at the grain boundaries. As a result, we obtained the finding that the tensile strength and reliability can be improved.
  • the inventors have found that the optimum mechanical strength can be given to the solder ball by adjusting the Bi content within a predetermined range. Further, the inventors have obtained the finding that when Bi is excessively added, the liquidus temperature decreases, ⁇ T increases, and the mechanical strength and the like decrease due to segregation.
  • the present inventors have found that by adjusting the Co content to a predetermined range, ⁇ T is reduced, the tensile strength is 50 MPa or more, and the elongation, Poisson's ratio, and coefficient of linear expansion can be improved.
  • the present invention has adopted the following configuration.
  • Ag 1.0 to 4.0% by mass
  • Cu 0.1 to 1.0% by mass
  • Bi 0.1 to 9.0% by mass
  • Ni 0.005 to 0.3% by mass
  • Ge A lead-free and antimony-free solder alloy having an alloy composition of 0.001 to 0.015% by mass and the balance of Sn.
  • solder alloy according to any one of [1] to [17], wherein the alloy composition satisfies 1 ⁇ Ag / Bi.
  • Ag and Bi each represent the content (mass%) in the alloy composition.
  • solder alloy according to any one of [1] to [17] and [22] to [25], wherein the alloy composition satisfies 1.2 ⁇ Ag / Bi ⁇ 3.0. Ag and Bi each represent the content (mass%) in the alloy composition.
  • Ag and Bi each represent the content (mass%) in the alloy composition.
  • a lead-free and antimony-free solder alloy having an alloy composition consisting of Sn.
  • solder alloy according to [34] Ag: 1.0 to 4.0% by mass, Cu: 0.7 to 1.0% by mass, Bi: 0.1 to 7.0% by mass, Ni: 0.040 to 0.095% by mass.
  • Ge A lead-free and antimony-free solder alloy having an alloy composition of 0.007 to 0.015% by mass and the balance of Sn.
  • the solder alloy according to [34] wherein the alloy composition contains Co: 0.001 to 0.1% by mass.
  • the solder alloy according to [34] or [35] which further satisfies 0.007 ⁇ Ni / (Ag + Bi) ⁇ 0.017.
  • Ni, Ag and Bi each represent the content (mass%) in the alloy composition.
  • Cu, Ni, Ag and Bi each represent the content (mass%) in the alloy composition.
  • [38] A solder ball made of the solder alloy according to any one of [1] to [37]. [39] The solder ball according to [38], which has an average particle size of 1 to 1000 ⁇ m. [40] The solder ball according to [38] or [39], which has a sphericity of 0.95 or more. [41] The solder ball according to any one of [38] to [40], which has a sphericity of 0.99 or more. [42] A Ball Grid Array formed by using the solder ball according to any one of [38] to [41]. [43] A solder joint made of the solder alloy according to any one of [1] to [37].
  • solder alloy a solder ball, and a solder joint having a melting point of about 230 ° C. and a tensile strength of 50 MPa or more.
  • the solder alloy according to the embodiment of the present invention has a melting point of around 230 ° C.
  • the main component is Sn having a melting point of 232 ° C.
  • the solder alloy according to the embodiment of the present invention has a melting point of around 230 ° C. even if it contains an element other than Sn.
  • the "melting point” of the solder alloy means the temperature of the solder alloy, which is equal to or higher than the solidus temperature and lower than the liquidus temperature.
  • Near 230 ° C means 170 to 230 ° C.
  • the melting point of the solder alloy is around 230 ° C means that "the solidus temperature of the solder alloy is 170 to 225 ° C and the liquidus temperature of the solder alloy is 210 to 230 ° C”. means.
  • solder alloy of this embodiment has Ag: 1.0 to 4.0% by mass, Cu: 0.1 to 1.0% by mass, Bi: 0.1 to 9.0% by mass, Ni: It has an alloy composition of 0.005 to 0.3% by mass, Ge: 0.001 to 0.015% by mass, and the balance of Sn, and is lead-free and antimony-free.
  • Ag 1.0 to 4.0% by mass Ag is an element that improves the strength of the solder alloy by precipitating fine Ag 3 Sn at the grain boundaries.
  • the Ag content is more preferably 2.0% by mass or more, and further preferably 3.0% by mass or more.
  • the Ag content is preferably 3.5% by mass or less.
  • the content of Ag is 1.0 to 4.0% by mass, preferably 1.0 to 3.5% by mass, more preferably 2.0 to 3.5% by mass, and 3 It is more preferably 0.0 to 3.5% by mass.
  • fine Ag 3 Sn can be sufficiently precipitated.
  • the Ag content is not more than the above upper limit value, the coarse amount of Ag 3 Sn precipitated can be reduced.
  • the strength of the joint portion after soldering can be increased.
  • the Ag content is not more than the upper limit value, the strength of the joint portion after soldering can be increased.
  • the Ag content is 3.5% by mass or less, the effect of reducing the precipitation amount of coarse Ag 3 Sn can be further enhanced.
  • Cu 0.1 to 1.0% by mass
  • the Cu content is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, and further preferably 0.75% by mass or more.
  • the Cu content is preferably 0.85% by mass or less, more preferably 0.8% by mass or less.
  • the Cu content is 0.1 to 1.0% by mass, preferably 0.5 to 0.85% by mass, more preferably 0.7 to 0.8% by mass, and 0. It is more preferably .75 to 0.8% by mass.
  • the thickness of the intermetallic compound layer at the bonding interface can be reduced by further setting the Cu content to 0.7% by mass or more.
  • the Cu content is not more than the upper limit, the thickness of the intermetallic compound layer at the bonding interface can be reduced.
  • the strength of the joint portion after soldering can be increased.
  • the Cu content is not more than the upper limit value, the strength of the joint portion after soldering can be increased.
  • the wettability can be improved.
  • the Cu content is preferably 0.7 to 1.0% by mass, more preferably 0.7 to 0.85% by mass, and preferably 0.75 to 0.8% by mass. More preferred.
  • the Bi content is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more.
  • the Bi content is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, and further preferably 3.0% by mass or less.
  • the Bi content is 0.1 to 9.0% by mass, preferably 0.2 to 5.0% by mass, more preferably 0.5 to 4.0% by mass, and 1 It is more preferably 0.0 to 3.0% by mass.
  • the Bi content is at least the above lower limit value, the optimum mechanical strength for the form of the solder ball used as the BGA can be obtained, and the creep resistance and the wettability can be improved.
  • Bi dissolves in Sn ( Cu, Ni), it distorts the crystal structure of 6Sn5 , suppresses Cu eating, and can sufficiently precipitate Cu 6Sn5 , which is a brittle SnNi compound. The amount of precipitation can be reduced.
  • the Bi content is not more than the upper limit value, it is possible to suppress an excessive decrease in the solid phase line temperature and narrow ⁇ T. As a result, segregation of Bi at the bonding interface is suppressed, and deterioration of mechanical strength and the like can be suppressed.
  • the Bi content is at least the above lower limit value, the strength of the joint portion after soldering can be increased.
  • the Bi content when the Bi content is 7.0% by mass or less, the strength of the joint portion after soldering can be increased. When the Bi content is at least the above lower limit value, the wettability can be improved.
  • the Bi content is preferably 0.1 to 7.0% by mass, more preferably 0.2 to 5% by mass, and even more preferably 0.5 to 4% by mass.
  • Ni 0.005 to 0.3% by mass
  • the Ni content is preferably 0.02% by mass or more, more preferably 0.03% by mass or more, and further preferably 0.04% by mass or more.
  • the Ni content is preferably 0.09% by mass or less, more preferably 0.08% by mass or less, and further preferably 0.06% by mass or less.
  • the Ni content is 0.005 to 0.3% by mass, preferably 0.02 to 0.09% by mass, more preferably 0.03 to 0.08% by mass, and 0. It is more preferably 0.04 to 0.06% by mass.
  • the Ni content is at least the above lower limit value, it is possible to control the liquidus temperature of the solder alloy and suppress Ni erosion as in the case of Cu.
  • the Ni content is not more than the upper limit value, it is possible to suppress an excessive increase in the liquidus temperature.
  • the Ni content is 0.04% by mass or more, so that the thickness of the intermetallic compound layer at the bonding interface can be reduced.
  • the strength of the joint portion after soldering can be increased.
  • the Ni content is 0.095% by mass or less, the thickness of the intermetallic compound layer at the bonding interface can be reduced.
  • the strength of the joint portion after soldering can be increased.
  • the Ni content is preferably 0.04 to 0.095% by mass, more preferably 0.04 to 0.08% by mass, and preferably 0.05 to 0.07% by mass. More preferred.
  • Ge 0.001 to 0.015% by mass
  • the content of Ge is preferably 0.002% by mass or more, and more preferably 0.003% by mass or more.
  • the content of Ge is preferably 0.012% by mass or less, more preferably 0.01% by mass or less, and further preferably 0.009% by mass or less.
  • the content of Ge is 0.001 to 0.015% by mass, preferably 0.002 to 0.012% by mass, more preferably 0.003 to 0.01% by mass, and 0. It is more preferably .003 to 0.009% by mass.
  • the movement of Ni to the solder alloy is hindered, it is possible to suppress Ni erosion.
  • the content of Ge is not more than the upper limit value, it is possible to suppress an excessive increase in the liquidus temperature.
  • the discoloration of the alloy can be suppressed by further setting the Ge content to 0.007% by mass or more.
  • the content of Ge is not more than the above upper limit value, the wettability can be improved.
  • the strength of the joint portion after soldering can be increased.
  • the content of Ge is preferably 0.007 to 0.015% by mass, more preferably 0.007 to 0.012% by mass, and preferably 0.007 to 0.009% by mass. More preferred.
  • the solder alloy of this embodiment may contain Co.
  • the content of Co is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, further preferably 0.004% by mass or more, and 0.006% by mass or more. Is particularly preferable.
  • the Co content is preferably 0.1% by mass or less, more preferably 0.015% by mass or less, further preferably 0.012% by mass or less, and 0.009% by mass or less. Is particularly preferable.
  • the content of Co is preferably 0.001 to 0.1% by mass, more preferably 0.002 to 0.015% by mass, and preferably 0.004 to 0.012% by mass.
  • the Co content is more preferably 0.006 to 0.009% by mass, and particularly preferably 0.006 to 0.009% by mass.
  • the Co content is within the above range, the tensile strength can be improved, and the elongation, Poisson's ratio, and linear expansion coefficient can be improved.
  • Sn The rest of the solder alloy of this embodiment is Sn.
  • unavoidable impurities may be contained. Even if it contains unavoidable impurities, it does not affect the above-mentioned effects. Specific examples of unavoidable impurities include As and Cd. Further, although the present invention is lead-free and antimony-free, it does not exclude the inclusion of Pb and Sb as unavoidable impurities.
  • Ag / Bi In the ratio represented by Ag / Bi, Ag and Bi each represent the content (% by mass) in the alloy composition.
  • the solder alloy of the present embodiment preferably satisfies 0.3 ⁇ Ag / Bi ⁇ 3.0.
  • Ag / Bi is within the above range, the tensile strength can be improved.
  • Ag / Bi ⁇ 1 may be used. In this case, the tensile strength can be further improved by setting 0.3 ⁇ Ag / Bi ⁇ 0.7.
  • the solder alloy of this embodiment does not contain Co, it may be 1 ⁇ Ag / Bi.
  • the solid phase temperature of the solder alloy of the present embodiment is 170 to 225 ° C., preferably 172 to 223 ° C., more preferably 174 to 221 ° C., and even more preferably 176 to 219 ° C. ..
  • the liquidus temperature of the solder alloy of the present embodiment is 210 to 230 ° C, preferably 212 to 230 ° C, more preferably 212 to 228 ° C, and further preferably 214 to 226 ° C. preferable.
  • ⁇ T is preferably 50 ° C. or lower, more preferably 45 ° C. or lower, further preferably 40 ° C. or lower, particularly preferably 30 ° C. or lower, and most preferably 15 ° C. or lower. preferable.
  • the lower limit of ⁇ T is not particularly limited, but may be, for example, 1 ° C.
  • Ni, Ag and Bi each represent the content (mass%) in the alloy composition.
  • Ni / (Ag + Bi) is Ni divided by the sum of Ag and Bi.
  • the solder alloy of the present embodiment preferably has Ni / (Ag + Bi) of more than 0.007. When 0.007 ⁇ Ni / (Ag + Bi), it is possible to suppress the coarsening of the intermetallic compound and to suppress an excessive decrease in the solid phase line temperature.
  • the solder alloy of the present embodiment preferably has Ni / (Ag + Bi) of less than 0.017. By setting Ni / (Ag + Bi) ⁇ 0.017, it is possible to suppress an excessive increase in the liquidus temperature. Thereby, the wettability can be made sufficient.
  • the solder alloy of this embodiment preferably satisfies 0.007 ⁇ Ni / (Ag + Bi) ⁇ 0.017.
  • (Cu / Ni) ⁇ (Ag + Bi) In the ratio here, Cu, Ni, Ag and Bi each represent the content (mass%) in the alloy composition.
  • (Cu / Ni) ⁇ (Ag + Bi) is the value obtained by dividing Cu by Ni and multiplying it by the sum of Ag and Bi.
  • the solder alloy of the present embodiment preferably has (Cu / Ni) ⁇ (Ag + Bi) of more than 46. By setting 46 ⁇ (Cu / Ni) ⁇ (Ag + Bi), it is possible to suppress an excessive increase in the liquidus temperature. Thereby, the wettability can be made sufficient.
  • the solder alloy of the present embodiment preferably has (Cu / Ni) ⁇ (Ag + Bi) of less than 120.
  • the solder alloy of the present embodiment preferably satisfies 46 ⁇ (Cu / Ni) ⁇ (Ag + Bi) ⁇ 120.
  • the solder alloy of the present embodiment may have a composition satisfying 46 ⁇ (Cu / Ni) ⁇ (Ag + Bi) ⁇ 110, or may have a composition satisfying 46 ⁇ (Cu / Ni) ⁇ (Ag + Bi) ⁇ 100. May be good.
  • solder alloy of the embodiment described above lead having a specific alloy composition consisting of Ag, Cu, Bi, Ni, Ge and Sn has a melting point of around 230 ° C. and a tensile strength of 50 MPa or more.
  • a free and antimony-free solder alloy can be provided.
  • ⁇ T can be reduced by keeping the contents of Ag and Bi within a predetermined range.
  • the solder alloy described above contains Co
  • ⁇ T can be reduced and the elongation of the solder alloy, the Poisson's ratio, and the coefficient of linear expansion can be improved. can.
  • solder alloy of this embodiment examples include those of the following first to fifth embodiments.
  • the solder alloy of the first embodiment has Ag: 1.0 to 4.0% by mass, Cu: 0.1 to 1.0% by mass, Bi: 0.1 to 9.0% by mass, Ni: 0.005. It is a lead-free and antimony-free solder alloy having an alloy composition of ⁇ 0.3% by mass, Ge: 0.001 to 0.015% by mass, and the balance of Sn, and 1 ⁇ Ag / Bi. Is.
  • the contents of Ag, Cu, Bi, Ni, and Ge may be those described above, respectively. In the ratio here, Ag and Bi each represent the content (mass%) in the alloy composition.
  • the solder alloy of the first embodiment has Ag: 3.5% by mass, Cu: 0.8% by mass, Bi: 1.0 to 2.0% by mass, Ni: 0.05% by mass, Ge: 0.008. It may be a lead-free and antimony-free solder alloy having an alloy composition of mass% and the balance of Sn.
  • the solder alloy of the first embodiment has Ag: 3.0 to 4.0% by mass, Cu: 0.7 to 0.9% by mass, Bi: 1.5% by mass, Ni: 0.03 to 0.08. It may be a lead-free and antimony-free solder alloy having an alloy composition of mass%, Ge: 0.006 to 0.009 mass%, and the balance of Sn.
  • the solder alloy of the first embodiment has Ag: 3.0 to 4.0% by mass, Cu: 0.7 to 0.9% by mass, Bi: 1.8% by mass, Ni: 0.03 to 0.08. It may be a lead-free and antimony-free solder alloy having an alloy composition of mass%, Ge: 0.006 to 0.009 mass%, and the balance of Sn.
  • the solder alloy of the first embodiment has Ag: 3.5% by mass, Cu: 0.8% by mass, Bi: 1.5 to 3.0% by mass, Ni: 0.05% by mass, Ge: 0.003. It may be a lead-free and antimony-free solder alloy having an alloy composition of mass% and the balance of Sn.
  • the solder alloy of the first embodiment has Ag: 3.0 to 4.0% by mass, Cu: 0.7 to 0.9% by mass, Bi: 2.0% by mass, Ni: 0.03 to 0.08. It may be a lead-free and antimony-free solder alloy having an alloy composition of mass%, Ge: 0.002 to 0.004 mass%, and the balance of Sn.
  • the solder alloy of the first embodiment has Ag: 3.0 to 4.0% by mass, Cu: 0.7 to 0.9% by mass, Bi: 2.5% by mass, Ni: 0.03 to 0.08. It may be a lead-free and antimony-free solder alloy having an alloy composition of mass%, Ge: 0.002 to 0.004 mass%, and the balance of Sn.
  • the solder alloy of the first embodiment preferably satisfies 1.2 ⁇ Ag / Bi ⁇ 3.0, and more preferably 1.3 ⁇ Ag / Bi ⁇ 1.9.
  • Ag and Bi each represent the content (mass%) in the alloy composition.
  • ⁇ T can be reduced and the tensile strength can be improved.
  • the solder alloy of the first embodiment has Ag: 3.5% by mass, Cu: 0.8% by mass, Bi: 1.5% by mass, Ni: 0.05% by mass, Ge: 0.008% by mass, and It may be a lead-free and antimony-free solder alloy having an alloy composition in which the balance is made of Sn.
  • the solder alloy of the first embodiment has Ag: 3.5% by mass, Cu: 0.8% by mass, Bi: 1.8% by mass, Ni: 0.05% by mass, Ge: 0.008% by mass, and It may be a lead-free and antimony-free solder alloy having an alloy composition in which the balance is made of Sn.
  • the solder alloy of the first embodiment has Ag: 3.5% by mass, Cu: 0.8% by mass, Bi: 2.0% by mass, Ni: 0.05% by mass, Ge: 0.003% by mass, and It may be a lead-free and antimony-free solder alloy having an alloy composition in which the balance is made of Sn.
  • the solder alloy of the first embodiment has Ag: 3.5% by mass, Cu: 0.8% by mass, Bi: 2.5% by mass, Ni: 0.05% by mass, Ge: 0.003% by mass, and It may be a lead-free and antimony-free solder alloy having an alloy composition in which the balance is made of Sn.
  • the solder alloy of the first embodiment has a specific alloy composition consisting of Ag, Cu, Bi, Ni, Ge and Sn, so that it has a melting point of around 230 ° C. and a tensile strength of 50 MPa or more, and is lead-free. Moreover, it is possible to provide an antimony-free solder alloy.
  • the solder alloy of the first embodiment can be applied not only to BGA but also to die bonding.
  • the solder alloy of the first embodiment has 1 ⁇ Ag / Bi. In the solder alloy of the first embodiment, ⁇ T can be reduced by keeping the contents of Ag and Bi within a predetermined range.
  • the solder alloy of the first embodiment preferably has a solid phase line temperature of 208 to 223 ° C, more preferably 210 to 221 ° C, and even more preferably 212 to 219 ° C.
  • the solder alloy of the first embodiment preferably has a liquidus temperature of 213 to 227 ° C, more preferably 215 to 225 ° C, and even more preferably 217 to 223 ° C.
  • ⁇ T is preferably 10 ° C. or lower, more preferably 8 ° C. or lower, and even more preferably 7 ° C. or lower.
  • the lower limit of ⁇ T is not particularly limited, but may be, for example, 1 ° C.
  • the solder alloy of the first embodiment preferably has 1.2 ⁇ Ag / Bi ⁇ 3.0, and more preferably 1.3 ⁇ Ag / Bi ⁇ 1.9.
  • the Ag / Bi ratio when the Ag / Bi ratio is within the above range, it becomes easy to reduce ⁇ T and to improve the tensile strength.
  • the solder alloy of the first embodiment preferably has 1.0 ⁇ Ag / Bi ⁇ 50.0, and more preferably 1.0 ⁇ Ag / Bi ⁇ 3.0. , 1.5 ⁇ Ag / Bi ⁇ 3.0 is more preferable.
  • the Ag / Bi ratio when the Ag / Bi ratio is within the above range, it becomes easy to reduce ⁇ T and to improve the tensile strength.
  • the solder alloy of the first embodiment is preferably 10.0 ⁇ Ag / Bi ⁇ 50.0, and more preferably 20.0 ⁇ Ag / Bi ⁇ 40.0. ..
  • the solder alloy of the first embodiment when the Ag / Bi ratio is within the above range, it becomes easy to reduce ⁇ T and to improve the tensile strength.
  • the solder alloy of the second embodiment has Ag: 1.0 to 4.0% by mass, Cu: 0.1 to 1.0% by mass, Bi: 0.1 to 9.0% by mass, Ni: 0.005. It is a lead-free and antimony-free solder alloy having an alloy composition of ⁇ 0.3% by mass, Ge: 0.001 to 0.015% by mass, and the balance of Sn, and satisfies Ag / Bi ⁇ 1. It is a thing.
  • the contents of Ag, Cu, Bi, Ni, and Ge may be those described above, respectively. In the ratio here, Ag and Bi each represent the content (mass%) in the alloy composition.
  • the solder alloy of the second embodiment has Ag: 2.0% by mass, Cu: 0.8% by mass, Bi: 3.0 to 5.0% by mass, Ni: 0.05% by mass, Ge: 0.008. It may be a lead-free and antimony-free solder alloy having an alloy composition of mass% and the balance of Sn.
  • the solder alloy of the second embodiment has Ag: 1.0 to 3.0% by mass, Cu: 0.7 to 0.9% by mass, Bi: 4.0% by mass, Ni: 0.04 to 0.08. It may be a lead-free and antimony-free solder alloy having an alloy composition of mass%, Ge: 0.006 to 0.009 mass%, and the balance of Sn.
  • the solder alloy of the second embodiment preferably satisfies 0.3 ⁇ Ag / Bi ⁇ 0.7.
  • Ag and Bi each represent the content (mass%) in the alloy composition.
  • the tensile strength can be further improved.
  • the solder alloy of the second embodiment has Ag: 2.0% by mass, Cu: 0.8% by mass, Bi: 4.0% by mass, Ni: 0.05% by mass, Ge: 0.008% by mass, and It is preferable that the solder alloy has an alloy composition in which the balance is Sn and is lead-free and antimony-free.
  • the solder alloy of the second embodiment has a specific alloy composition consisting of Ag, Cu, Bi, Ni, Ge and Sn, so that it has a melting point of around 230 ° C. and a tensile strength of 50 MPa or more, and is lead-free. Moreover, it is possible to provide an antimony-free solder alloy.
  • the solder alloy of the second embodiment can be applied not only to BGA but also to die bonding.
  • the solder alloy of the second embodiment has Ag / Bi ⁇ 1. In the solder alloy of the second embodiment, ⁇ T can be reduced by keeping the contents of Ag and Bi within a predetermined range.
  • the solder alloy of the second embodiment preferably has a solid phase line temperature of 175 to 220 ° C, more preferably 175 to 218 ° C, and even more preferably 176 to 216 ° C.
  • the solder alloy of the second embodiment has a liquidus temperature of 210 to 230 ° C, preferably 211 to 229 ° C, and more preferably 213 to 227 ° C.
  • ⁇ T is preferably 50 ° C. or lower, more preferably 45 ° C. or lower, and even more preferably 40 ° C. or lower.
  • the lower limit of ⁇ T is not particularly limited, but may be, for example, 1 ° C.
  • the solder alloy of the second embodiment is preferably 0.3 ⁇ Ag / Bi ⁇ 0.7.
  • the solder alloy of the second embodiment when the Ag / Bi ratio is within the above range, it becomes easy to reduce ⁇ T and to improve the tensile strength.
  • the solder alloy of the second embodiment preferably has 0.1 ⁇ Ag / Bi ⁇ 0.8, and more preferably 0.15 ⁇ Ag / Bi ⁇ 0.7. , 0.2 ⁇ Ag / Bi ⁇ 0.6 is more preferable.
  • the Ag / Bi ratio when the Ag / Bi ratio is within the above range, it becomes easy to reduce ⁇ T and to improve the tensile strength.
  • the solder alloy of the first embodiment can suppress a decrease in the solid phase line temperature as compared with the solder alloy of the second embodiment.
  • the solder alloy of the first embodiment can reduce ⁇ T as compared with the solder alloy of the second embodiment.
  • the solder alloy of the second embodiment can improve the tensile strength as compared with the solder alloy of the first embodiment.
  • the solder alloy of the third embodiment has Ag: 1.0 to 4.0% by mass, Cu: 0.1 to 1.0% by mass, Bi: 0.1 to 9.0% by mass, Ni: 0.005. It has an alloy composition of ⁇ 0.3% by mass, Ge: 0.001 to 0.015% by mass, Co: 0.001 to 0.1% by mass, and the balance of Sn, and is lead-free and antimony-free. It is a solder alloy.
  • the contents of Ag, Cu, Bi, Ni, Ge, and Co may be those described above, respectively.
  • the solder alloy of the third embodiment has Ag: 3.5% by mass, Cu: 0.8% by mass, Bi: 0.3 to 0.7% by mass, Ni: 0.05% by mass, Ge: 0.008. It may be a lead-free and antimony-free solder alloy having an alloy composition of mass%, Co: 0.008 mass%, and the balance of Sn.
  • the solder alloy of the third embodiment has Ag: 3.0 to 4.0% by mass, Cu: 0.7 to 0.9% by mass, Bi: 0.5% by mass, Ni: 0.03 to 0.08. It is a lead-free and antimony-free solder alloy having an alloy composition consisting of mass%, Ge: 0.006 to 0.009 mass%, Co: 0.004 to 0.012 mass%, and the balance of Sn. You may.
  • the solder alloy of the third embodiment has Bi: 0.3 to 1.0% by mass, and more preferably 5 ⁇ Ag / Bi ⁇ 15.
  • Ag and Bi each represent the content (mass%) in the alloy composition.
  • the solder alloy of the third embodiment has Ag: 3.5% by mass, Cu: 0.8% by mass, Bi: 0.5% by mass, Ni: 0.05% by mass, Ge: 0.008% by mass, Co. : It is preferable that the solder alloy has an alloy composition of 0.008% by mass and the balance is Sn, and is lead-free and antimony-free.
  • the solder alloy of the third embodiment has a Co content of 0.001 to 0.1% by mass.
  • the solder alloy of the third embodiment has a specific alloy composition consisting of Ag, Cu, Bi, Ni, Ge, Co and Sn, so that the melting point is around 230 ° C. and the tensile strength is 50 MPa or more. Lead-free and antimony-free solder alloys can be provided.
  • the solder alloy of the third embodiment can be applied not only to BGA but also to die bonding.
  • the solder alloy of the third embodiment preferably has a solid phase line temperature of 212 to 222 ° C, more preferably 214 to 220 ° C, and even more preferably 216 to 218 ° C.
  • the solder alloy of the third embodiment preferably has a liquidus temperature of 216 to 226 ° C, more preferably 218 to 224 ° C, and even more preferably 220 to 222 ° C.
  • ⁇ T is preferably 10 ° C. or lower, more preferably 8 ° C. or lower, and even more preferably 7 ° C. or lower.
  • the lower limit of ⁇ T is not particularly limited, but may be, for example, 1 ° C.
  • the solder alloy of the third embodiment preferably has 5 ⁇ Ag / Bi ⁇ 15.
  • the solder alloy of the third embodiment when the Ag / Bi ratio is within the above range, it becomes easy to reduce ⁇ T and to improve the tensile strength. Further, in the solder alloy of the third embodiment, when the Ag / Bi ratio is within the above range, the elongation, Poisson's ratio and the coefficient of linear expansion can be improved.
  • the solder alloy of the third embodiment preferably has 0.2 ⁇ Ag / Bi ⁇ 15.0, and more preferably 0.3 ⁇ Ag / Bi ⁇ 3.0. , 0.5 ⁇ Ag / Bi ⁇ 2.0 is more preferable, and 0.6 ⁇ Ag / Bi ⁇ 1.0 is particularly preferable.
  • the Ag / Bi ratio when the Ag / Bi ratio is within the above range, it becomes easy to reduce ⁇ T and to improve the tensile strength.
  • the solder alloy of the third embodiment preferably has a solid phase line temperature of 200 to 223 ° C, more preferably 202 to 221 ° C, and even more preferably 204 to 219 ° C.
  • the solder alloy of the third embodiment preferably has a liquidus temperature of 210 to 227 ° C, more preferably 211 to 225 ° C, and more preferably 213 to 223 ° C.
  • ⁇ T is preferably 30 ° C. or lower, more preferably 20 ° C. or lower, and even more preferably 15 ° C. or lower.
  • the lower limit of ⁇ T is not particularly limited, but may be, for example, 1 ° C.
  • the solder alloy of the fourth embodiment has Ag: 1.0 to 4.0% by mass, Cu: 0.7 to 1.0% by mass, Bi: 0.1 to 7.0% by mass, Ni: 0.040. It is a lead-free and antimony-free solder alloy having an alloy composition of ⁇ 0.095% by mass, Ge: 0.007 to 0.015% by mass, and the balance of Sn.
  • the contents of Ag, Cu, Bi, Ni, and Ge may be those described above, respectively.
  • the solder alloy of the fourth embodiment has Ag: 3.0 to 3.5% by mass, Cu: 0.7 to 1.0% by mass, Bi: 1.0 to 2.0% by mass, Ni: 0.040. It may be a lead-free and antimony-free solder alloy having an alloy composition of up to 0.060% by mass, Ge: 0.007 to 0.010% by mass, and the balance of Sn.
  • the solder alloy of the fourth embodiment has Ag: 1.5 to 2.5% by mass, Cu: 0.7 to 1.0% by mass, Bi: 3.0 to 5.0% by mass, Ni: 0. It may be a lead-free and antimony-free solder alloy having an alloy composition of 060 to 0.080% by mass, Ge: 0.007 to 0.010% by mass, and the balance of Sn.
  • the solder alloy of the fourth embodiment has a specific alloy composition consisting of Ag, Cu, Bi, Ni, Ge and Sn, so that it has a melting point of around 230 ° C. and a tensile strength of 50 MPa or more, and is lead-free. Moreover, it is possible to provide an antimony-free solder alloy.
  • the solder alloy of the fourth embodiment can be applied not only to BGA but also to die bonding.
  • the solder alloy of the fourth embodiment preferably has 0.3 ⁇ Ag / Bi ⁇ 3.0, more preferably 1.2 ⁇ Ag / Bi ⁇ 3.0, and 1.3 ⁇ Ag /. It is more preferable that Bi ⁇ 1.9.
  • ⁇ T can be easily reduced and the tensile strength can be easily improved.
  • the solder alloy of the fourth embodiment preferably has 0.3 ⁇ Ag / Bi ⁇ 3.0, and more preferably 0.3 ⁇ Ag / Bi ⁇ 0.7.
  • the Ag / Bi ratio is within the above range, ⁇ T can be easily reduced and the tensile strength can be easily improved.
  • the solder alloy of the fourth embodiment further has the following effects.
  • the solder alloy of the fourth embodiment can reduce the thickness of the intermetallic compound layer at the bonding interface. Further, the solder alloy of the fourth embodiment can sufficiently precipitate fine Ag 3 Sn, and can reduce the amount of coarse Ag 3 Sn deposited. Further, the solder alloy of the fourth embodiment can suppress discoloration of the alloy. Further, the solder alloy of the fourth embodiment can increase the strength of the joint portion after soldering.
  • the solder alloy of the fourth embodiment preferably has Ni / (Ag + Bi) of more than 0.007.
  • Ni / (Ag + Bi) When 0.007 ⁇ Ni / (Ag + Bi), it is possible to suppress the coarsening of the intermetallic compound and to suppress an excessive decrease in the solid phase line temperature.
  • the solder alloy of the fourth embodiment preferably has Ni / (Ag + Bi) of less than 0.017. By setting Ni / (Ag + Bi) ⁇ 0.017, it is possible to suppress an excessive increase in the liquidus temperature. Thereby, the wettability can be made sufficient.
  • the solder alloy of the fourth embodiment preferably satisfies 0.007 ⁇ Ni / (Ag + Bi) ⁇ 0.017. Ni, Ag and Bi each represent the content (mass%) in the alloy composition.
  • the solder alloy of the fourth embodiment preferably has (Cu / Ni) ⁇ (Ag + Bi) of more than 46. By setting 46 ⁇ (Cu / Ni) ⁇ (Ag + Bi), it is possible to suppress an excessive increase in the liquidus temperature. Thereby, the wettability can be made sufficient.
  • the solder alloy of the fourth embodiment preferably has (Cu / Ni) ⁇ (Ag + Bi) of less than 120. By setting (Cu / Ni) ⁇ (Ag + Bi) ⁇ 120, it is possible to suppress the coarsening of the intermetallic compound and to suppress an excessive decrease in the solid phase line temperature.
  • the solder alloy of the fourth embodiment preferably satisfies 46 ⁇ (Cu / Ni) ⁇ (Ag + Bi) ⁇ 120.
  • the solder alloy of the fourth embodiment may have a composition satisfying 46 ⁇ (Cu / Ni) ⁇ (Ag + Bi) ⁇ 110, or may have a composition satisfying 46 ⁇ (Cu / Ni) ⁇ (Ag + Bi) ⁇ 100. You may.
  • the solder alloy of the fourth embodiment preferably has 1.0 ⁇ Ag / Bi ⁇ 50.0, more preferably 1.0 ⁇ Ag / Bi ⁇ 3.0, and 1.5 ⁇ Ag /. It is more preferable that Bi ⁇ 3.0.
  • ⁇ T can be easily reduced and the tensile strength can be easily improved.
  • the solder alloy of the fourth embodiment is preferably 10.0 ⁇ Ag / Bi ⁇ 50.0, and more preferably 20.0 ⁇ Ag / Bi ⁇ 40.0. ..
  • the solder alloy of the fourth embodiment when the Ag / Bi ratio is within the above range, ⁇ T can be easily reduced and the tensile strength can be easily improved.
  • the solder alloy of the fourth embodiment preferably has 0.1 ⁇ Ag / Bi ⁇ 0.8, more preferably 0.15 ⁇ Ag / Bi ⁇ 0.7, and 0.2 ⁇ . It is more preferable that Ag / Bi ⁇ 0.6.
  • the Ag / Bi ratio when the Ag / Bi ratio is within the above range, ⁇ T can be easily reduced and the tensile strength can be easily improved.
  • the solder alloy of the fourth embodiment has a solid phase line temperature of 170 to 225 ° C, preferably 172 to 223 ° C, more preferably 174 to 221 ° C, and more preferably 176 to 219 ° C. More preferred.
  • the solder alloy of the fourth embodiment has a liquidus temperature of 210 to 230 ° C, preferably 212 to 230 ° C, more preferably 212 to 228 ° C, and 214 to 226 ° C. Is more preferable.
  • ⁇ T is preferably 50 ° C. or lower, more preferably 45 ° C. or lower, and even more preferably 40 ° C. or lower.
  • the lower limit of ⁇ T is not particularly limited, but may be, for example, 1 ° C.
  • the solder alloy of the fifth embodiment has Ag: 1.0 to 4.0% by mass, Cu: 0.7 to 1.0% by mass, Bi: 0.1 to 7.0% by mass, Ni: 0.040. It has an alloy composition of ⁇ 0.095% by mass, Ge: 0.007 to 0.015% by mass, Co: 0.001 to 0.1% by mass, and the balance of Sn, and is lead-free and antimony-free. It is a solder alloy.
  • the contents of Ag, Cu, Bi, Ni, Ge, and Co may be those described above, respectively.
  • the solder alloy of the fifth embodiment has Ag: 3.0 to 3.5% by mass, Cu: 0.7 to 1.0% by mass, Bi: 0.3 to 0.7% by mass, Ni: 0.040. It has an alloy composition of ⁇ 0.060% by mass, Ge: 0.007 to 0.010% by mass, Co: 0.005 to 0.010% by mass, and the balance of Sn, and is lead-free and antimony-free. It may be a solder alloy.
  • the solder alloy of the fifth embodiment has a specific alloy composition consisting of Ag, Cu, Bi, Ni, Ge, Co and Sn, so that the melting point is around 230 ° C. and the tensile strength is 50 MPa or more. Lead-free and antimony-free solder alloys can be provided.
  • the solder alloy of the fifth embodiment can be applied not only to BGA but also to die bonding.
  • the solder alloy of the fifth embodiment can improve elongation, Poisson's ratio, and coefficient of linear expansion.
  • the solder alloy of the fifth embodiment preferably has 5 ⁇ Ag / Bi ⁇ 15.
  • ⁇ T can be easily reduced and the tensile strength can be easily improved. It also facilitates improvement of elongation, Poisson's ratio, and coefficient of linear expansion.
  • the solder alloy of the fifth embodiment further has the following effects.
  • the solder alloy of the fifth embodiment can reduce the thickness of the intermetallic compound layer at the bonding interface.
  • the solder alloy of the fifth embodiment can sufficiently precipitate fine Ag 3 Sn, and can reduce the amount of coarse Ag 3 Sn deposited.
  • the solder alloy of the fifth embodiment can suppress discoloration of the alloy.
  • the solder alloy of the fifth embodiment can increase the strength of the joint portion after soldering.
  • the solder alloy of the fifth embodiment preferably has Ni / (Ag + Bi) of more than 0.007.
  • Ni / (Ag + Bi) When 0.007 ⁇ Ni / (Ag + Bi), it is possible to suppress the coarsening of the intermetallic compound and to suppress an excessive decrease in the solid phase line temperature.
  • the solder alloy of the fifth embodiment preferably has Ni / (Ag + Bi) of less than 0.017. By setting Ni / (Ag + Bi) ⁇ 0.017, it is possible to suppress an excessive increase in the liquidus temperature. Thereby, the wettability can be made sufficient.
  • the solder alloy of the fifth embodiment preferably satisfies 0.007 ⁇ Ni / (Ag + Bi) ⁇ 0.017. Ni, Ag and Bi each represent the content (mass%) in the alloy composition.
  • the solder alloy of the fifth embodiment preferably has (Cu / Ni) ⁇ (Ag + Bi) of more than 46. By setting 46 ⁇ (Cu / Ni) ⁇ (Ag + Bi), it is possible to suppress an excessive increase in the liquidus temperature. Thereby, the wettability can be made sufficient.
  • the solder alloy of the fifth embodiment preferably has (Cu / Ni) ⁇ (Ag + Bi) of less than 120. By setting (Cu / Ni) ⁇ (Ag + Bi) ⁇ 120, it is possible to suppress the coarsening of the intermetallic compound and to suppress an excessive decrease in the solid phase line temperature.
  • the solder alloy of the fifth embodiment preferably satisfies 46 ⁇ (Cu / Ni) ⁇ (Ag + Bi) ⁇ 120.
  • the solder alloy of the fifth embodiment may have a composition satisfying 46 ⁇ (Cu / Ni) ⁇ (Ag + Bi) ⁇ 110, or may have a composition satisfying 46 ⁇ (Cu / Ni) ⁇ (Ag + Bi) ⁇ 100. You may.
  • the solder alloy of the fifth embodiment is preferably 0.2 ⁇ Ag / Bi ⁇ 15.0, and more preferably 5 ⁇ Ag / Bi ⁇ 15.
  • ⁇ T can be easily reduced and the tensile strength can be easily improved.
  • the elongation, Poisson's ratio and the coefficient of linear expansion can be improved.
  • the solder alloy of the fifth embodiment preferably has 0.2 ⁇ Ag / Bi ⁇ 15.0, more preferably 0.3 ⁇ Ag / Bi ⁇ 3.0, and 0.5 ⁇ .
  • Ag / Bi ⁇ 2.0 is more preferable, and 0.6 ⁇ Ag / Bi ⁇ 1.0 is particularly preferable.
  • ⁇ T can be easily reduced and the tensile strength can be easily improved.
  • the solder alloy of the fifth embodiment preferably has a solid phase line temperature of 200 to 223 ° C, more preferably 202 to 221 ° C, and even more preferably 204 to 219 ° C.
  • the solder alloy of the fifth embodiment preferably has a liquidus temperature of 210 to 227 ° C, more preferably 211 to 225 ° C, and more preferably 213 to 223 ° C.
  • ⁇ T is preferably 30 ° C. or lower, more preferably 20 ° C. or lower, and even more preferably 15 ° C. or lower.
  • the lower limit of ⁇ T is not particularly limited, but may be, for example, 1 ° C.
  • solder balls The lead-free and antimony-free solder alloys of the embodiments described above are most suitable for the form of solder balls used in BGA.
  • the sphericity of the solder ball of the present embodiment is preferably 0.90 or more, more preferably 0.95 or more, and most preferably 0.99 or more.
  • the sphericity is obtained by various methods such as the least squares center method (LSC method), the minimum region center method (MZC method), the maximum inscribed center method (MIC method), and the minimum circumscribed center method (MCC method). ..
  • the sphericity of the solder ball is measured by using a CNC image measuring system (Ultra Quick Vision ULTRA QV350-PRO measuring device manufactured by Mitutoyo Co., Ltd.) using the minimum region center method (MZC method).
  • the sphericity represents a deviation from the true sphere, and is, for example, an arithmetic mean value calculated when the diameter of each of 500 balls is divided by the major axis, and the value is 1.00, which is the upper limit. The closer it is, the closer it is to a true sphere.
  • the solder balls of the present embodiment are used for forming bumps on electrodes and substrates of semiconductor packages such as BGA (ball grid array).
  • the diameter of the solder ball according to the present embodiment is preferably in the range of 1 to 1000 ⁇ m, more preferably 50 ⁇ m or more and 300 ⁇ m.
  • the solder ball can be manufactured by a general solder ball manufacturing method.
  • the diameter in the present embodiment means the diameter measured by Mitutoyo's Ultra Quick Vision ULTRA QV350-PRO measuring device.
  • solder joint of the present embodiment is suitable for connection between an IC chip and its substrate (interposer) in a semiconductor package, or for connection between a semiconductor package and a printed wiring board.
  • the "solder joint" according to the present invention is connected by using the above-mentioned solder alloy according to the present invention, and means a connection portion between an IC chip and a substrate, and a connection portion between electrodes or a die and a substrate. Including the connection part of.
  • the joining method using the solder alloy of the above-described embodiment may be performed according to a conventional method using, for example, a reflow method.
  • the heating temperature may be appropriately adjusted according to the heat resistance of the chip and the liquidus temperature of the solder alloy.
  • the temperature is preferably about 240 ° C. from the viewpoint of suppressing thermal damage to the chip to a low level.
  • the melting temperature of the solder alloy in the case of flow soldering may be about 20 ° C. higher than the liquidus temperature.
  • the structure can be further made finer by considering the cooling rate at the time of solidification. For example, the solder joint is cooled at a cooling rate of 2 to 3 ° C./s or higher.
  • Other joining conditions can be appropriately adjusted according to the alloy composition of the solder alloy.
  • the solder alloy according to the present invention can be produced as a low ⁇ -dose alloy by using a low ⁇ -dose material as a raw material thereof.
  • a low ⁇ -dose alloy is used for forming solder bumps around a memory, it is possible to suppress soft errors.
  • solder alloys of Examples 1 to 4 were synthesized with the composition shown below. Each solder alloy was measured by the method shown below.
  • the solid-phase line temperature and liquid-phase line temperature are measured by differential scanning calorimetry (DSC) using a thermomechanical analyzer (EXSTAR 6000, Seiko Instruments). It was measured by the method according to calorimetry).
  • the solid phase temperature was measured by a method according to JIS Z3198-1.
  • the liquidus temperature was measured by a DSC method similar to the method for measuring the solidus temperature of JIS Z3198-1.
  • Example 1 An alloy composition consisting of Ag: 3.5% by mass, Cu: 0.8% by mass, Bi: 1.5% by mass, Ni: 0.05% by mass, Ge: 0.008% by mass, and the balance of Sn.
  • the solder alloy of Example 1 had a solid phase line temperature of 214 ° C., a liquidus line temperature of 219 ° C., and ⁇ T of 5 ° C.
  • the solder alloy of Example 1 had a tensile strength of 66.2 MPa.
  • Example 2 An alloy composition consisting of Ag: 3.5% by mass, Cu: 0.8% by mass, Bi: 1.8% by mass, Ni: 0.05% by mass, Ge: 0.008% by mass, and the balance of Sn.
  • the solder alloy of Example 2 had a solid phase temperature of 213 ° C, a liquidus temperature of 218 ° C, and ⁇ T of 5 ° C.
  • the solder alloy of Example 2 had a tensile strength of 69.9 MPa.
  • Example 3 An alloy composition consisting of Ag: 2.0% by mass, Cu: 0.75% by mass, Bi: 4.0% by mass, Ni: 0.07% by mass, Ge: 0.008% by mass, and the balance of Sn.
  • the solder alloy of Example 3 had a solid phase line temperature of 206 ° C., a liquidus line temperature of 219 ° C., and ⁇ T of 13 ° C.
  • the solder alloy of Example 3 had a tensile strength of 83.8 MPa.
  • Example 4 Ag: 3.5% by mass, Cu: 0.8% by mass, Bi: 0.5% by mass, Ni: 0.05% by mass, Ge: 0.008% by mass, Co: 0.008% by mass, and A solder alloy having an alloy composition in which the balance is made of Sn was produced.
  • the solder alloy of Example 4 had a solid phase temperature of 217 ° C, a liquidus temperature of 221 ° C, and ⁇ T of 4 ° C.
  • the solder alloy of Example 4 had a tensile strength of 55.5 MPa.
  • the solder alloy of Example 4 had an elongation of 33%.
  • the solder alloy of Example 4 had a Poisson's ratio of 0.35.
  • the solder alloy of Example 4 had a coefficient of linear expansion of 21.5 ppm / K.
  • Example 5 An alloy composition consisting of Ag: 3.5% by mass, Cu: 0.8% by mass, Bi: 2.0% by mass, Ni: 0.05% by mass, Ge: 0.003% by mass, and the balance of Sn.
  • the solder alloy of Example 5 had a solid phase line temperature of 212 ° C., a liquidus line temperature of 218 ° C., and ⁇ T of 6 ° C.
  • the solder alloy of Example 5 had a tensile strength of 72.3 MPa.
  • Example 6 An alloy composition consisting of Ag: 3.5% by mass, Cu: 0.8% by mass, Bi: 2.5% by mass, Ni: 0.05% by mass, Ge: 0.003% by mass, and the balance of Sn.
  • the solder alloy of Example 6 had a solid phase line temperature of 211 ° C., a liquidus line temperature of 216 ° C., and ⁇ T of 5 ° C.
  • the solder alloy of Example 6 had a tensile strength of 78.0 MPa.
  • solder alloy powder of the test example was prepared with the compositions shown in Tables 1 to 5 below.
  • the solder alloy powder has a size (particle size distribution) that satisfies the symbol 6 in the powder size classification (Table 2) in JIS Z 3284-1: 2014.
  • the mass fraction of the powder having a particle size of 5 to 15 ⁇ m is 80% or more with respect to the mass (100%) of the entire solder alloy powder.
  • Test Examples A1 to A12 and Test Example A14 correspond to the fourth embodiment.
  • Test Example A13 and Test Example A15 correspond to the fifth embodiment.
  • Test Examples B1 to B16 do not fall under any of the fourth and fifth embodiments.
  • Test Examples B3, Test Examples B5 to B6, Test Examples B8 to B9, and Test Examples B11 to B16 are within the scope of the present invention.
  • Test Examples B1 to B2, Test Example B4, Test Example B7, and Test Example B10 are outside the scope of the present invention.
  • an electrode pattern (S / F: Cu-OSP) was printed on a glass epoxy substrate (FR-4, size 30 ⁇ 120 mm, thickness 0.8 mm) using solder paste.
  • the solder alloy powder contained in the solder paste was a solder alloy in which Ag was 3% by mass, Cu was 0.5% by mass, and the balance was Sn.
  • an evaluation substrate was produced by performing reflow soldering (220 ° C. or higher, 40 seconds, peak temperature 245 ° C.) using the above-mentioned CSP with solder ball electrodes and a glass epoxy substrate after printing.
  • test Examples A1 to A15 and Test Examples B1 to B16 are shown in Tables 1 and 2.
  • A The thickness of the IMC layer is less than 1.4 ⁇ m.
  • B The thickness of the IMC layer is 1.4 ⁇ m or more.
  • A The maximum length of Ag 3 Sn is less than 5 ⁇ m.
  • B The maximum length of Ag 3 Sn is 5 ⁇ m or more and less than 90 ⁇ m.
  • C The maximum length of Ag 3 Sn is 90 ⁇ m or more.
  • A The solder ball is discolored.
  • B The solder ball is not discolored.
  • A The wet spread length is 1000 ⁇ m or more.
  • B Wet spread length is less than 1000 ⁇ m.
  • A The ratio of the number of tests in which the IMC layer was destroyed was 50% or less of the total number of tests.
  • B The ratio of the number of tests in which the IMC layer was destroyed was more than 50% of the total number of tests.
  • Test Examples A1 to A15 corresponding to the 4th embodiment or the 5th embodiment, the evaluation of the thickness of the IMC layer was A. Further, Test Examples B1 to B2 and Test Examples B7 to B16 having a Cu content of 0.7 to 1.0% by mass and a Ni content of 0.040 to 0.095% by mass or less. The evaluation of the thickness of the IMC layer was A. On the other hand, in Test Examples B3 to B6 in which the content of Cu or Ni was out of the above range, the evaluation of the thickness of the IMC layer was B.
  • Test Examples A1 to A15 corresponding to the 4th embodiment or the 5th embodiment, the evaluation of the size of Ag 3 Sn was A or B.
  • Test Example A1 Test Examples A3 to A14, Test Example B1, and Test Examples B3 to B15 having an Ag content of 3.5% by mass or less
  • the evaluation of the size of Ag 3 Sn was A.
  • Test Example A2 and Test Example B16 in which the Ag content was 4.0% by mass
  • the evaluation of the size of Ag 3 Sn was B.
  • Test Example B2 in which the Ag content was more than 4.0% by mass, the evaluation of the size of Ag 3 Sn was C.
  • test Examples A1 to A15 corresponding to the 4th embodiment or the 5th embodiment, the evaluation of discoloration resistance was A. Further, in Test Examples B1 to B8 and Test Examples B10 to B12 having a Ge content of 0.007% by mass or more, the evaluation of discoloration resistance was A. On the other hand, in Test Examples B9 and B13 to B16 in which the Ge content was less than 0.007% by mass, the evaluation of discoloration resistance was B.
  • Test Examples A1 to A15 corresponding to the 4th embodiment or the 5th embodiment, the evaluation of wettability was A.
  • Test Examples B2 to B3, B5, and B8 to B9 the wettability was evaluated as A.
  • Test Example B1, Test Example B6, and Test Examples B11 to B13 in which 0.017 ⁇ Ni / (Ag + Bi) and (Cu / Ni) ⁇ (Ag + Bi) ⁇ 46, are evaluated for wettability.
  • Test Example B4 in which the Cu content was more than 1.0% by mass, the wettability was evaluated as B.
  • Test Example B7 in which the Bi content was less than 0.1% by mass, the wettability was evaluated as B.
  • Test Example B10 having a Ge content of more than 0.015% by mass the wettability was evaluated as B.
  • Test Example B14 in which the content of Ag or Bi was not sufficient, the wettability was evaluated as B.
  • Test Examples A1 to A15 corresponding to the 4th embodiment or the 5th embodiment, the evaluation of the strength of the solder joint portion was A. Further, Ag: 1.0 to 4.0% by mass, Cu: 0.7 to 1.0% by mass, Bi: 0.1 to 7.0% by mass, Ni: 0.040 to 0.095% by mass, In Test Examples B1 to B8, Test Examples B9, and Test Examples B11 to B16 having Ge: 0.015% by mass or less, the evaluation of the strength of the solder joint was A. On the other hand, in Test Examples B1 and B2 in which the Ag content was out of the above range, the evaluation of the strength of the solder joint was B.
  • test Examples B3 and B4 in which the Cu content was out of the above range, the evaluation of the strength of the solder joint portion was B. Further, in Test Examples B5 and B6 in which the Ni content was out of the above range, the evaluation of the strength of the solder joint was B. Further, in Test Examples B7 and B8 in which the Bi content was out of the predetermined range, the evaluation of the strength of the solder joint portion was B. Further, in Test Example B10 in which the Ge content was more than 0.015% by mass, the evaluation of the strength of the solder joint portion was B.
  • the solder alloys of the 4th embodiment and the 5th embodiment have the following effects.
  • the solder alloy can reduce the thickness of the intermetallic compound layer at the bonding interface. Further, the solder alloy can sufficiently precipitate fine Ag 3 Sn and can reduce the amount of coarse Ag 3 Sn deposited. Further, the solder alloy of the fifth embodiment can suppress discoloration of the alloy. Further, the solder alloy of the fifth embodiment can increase the strength of the joint portion after soldering. The solder alloy can improve the wettability.
  • test Examples A1 to A15 had a melting point of around 230 ° C. and a tensile strength of 50 MPa or more.
  • solder alloy a solder ball, and a solder joint having a melting point of about 230 ° C. and a tensile strength of 50 MPa or more.
  • the solder alloy, solder ball, and solder joint can be suitably used for QFP.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)
  • Connection Of Batteries Or Terminals (AREA)
PCT/JP2021/042233 2020-11-19 2021-11-17 はんだ合金、はんだボール、及びはんだ継手 Ceased WO2022107806A1 (ja)

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KR1020237016199A KR102901735B1 (ko) 2020-11-19 2021-11-17 땜납 합금, 땜납 볼, 및 땜납 이음
JP2022517181A JP7100283B1 (ja) 2020-11-19 2021-11-17 はんだ合金、はんだボール、及びはんだ継手
MYPI2023001946A MY199315A (en) 2020-11-19 2021-11-17 Solder alloy, solder ball and solder joint
EP24196170.5A EP4578592A1 (en) 2020-11-19 2021-11-17 Solder alloy, solder ball and solder joint
KR1020257041766A KR20260004560A (ko) 2020-11-19 2021-11-17 땜납 합금, 땜납 볼, 및 땜납 이음
US18/033,750 US12583060B2 (en) 2020-11-19 2021-11-17 Solder alloy, solder ball and solder joint
EP21894680.4A EP4249165A4 (en) 2020-11-19 2021-11-17 Solder alloy, solder ball and solder joint
MX2023005700A MX2023005700A (es) 2020-11-19 2021-11-17 Aleacion de soldadura, bola de soldadura y junta de soldadura.
CA3198256A CA3198256C (en) 2020-11-19 2021-11-17 WELDING ALLOY, WELDING GLOBE, AND SOFT BRAZING JOINT
CN202180077121.4A CN116472140A (zh) 2020-11-19 2021-11-17 焊料合金、焊球及焊料接头
JP2022097574A JP7144708B2 (ja) 2020-11-19 2022-06-16 はんだ合金、はんだボール、及びはんだ継手
JP2022097573A JP2022130498A (ja) 2020-11-19 2022-06-16 はんだ合金、はんだボール、及びはんだ継手

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KR102901735B1 (ko) 2025-12-19
JP7100283B1 (ja) 2022-07-13
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US12583060B2 (en) 2026-03-24
EP4249165A4 (en) 2024-05-15
EP4249165A1 (en) 2023-09-27
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MX2023011401A (es) 2023-10-12
TWI833132B (zh) 2024-02-21
EP4578592A1 (en) 2025-07-02
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US20230398643A1 (en) 2023-12-14
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CA3198256C (en) 2025-05-06
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