JP5722302B2 - Lead-free solder alloy, solder paste using this, and mounted product - Google Patents
Lead-free solder alloy, solder paste using this, and mounted product Download PDFInfo
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- JP5722302B2 JP5722302B2 JP2012500457A JP2012500457A JP5722302B2 JP 5722302 B2 JP5722302 B2 JP 5722302B2 JP 2012500457 A JP2012500457 A JP 2012500457A JP 2012500457 A JP2012500457 A JP 2012500457A JP 5722302 B2 JP5722302 B2 JP 5722302B2
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- 229910000679 solder Inorganic materials 0.000 title claims description 92
- 229910045601 alloy Inorganic materials 0.000 title claims description 54
- 239000000956 alloy Substances 0.000 title claims description 54
- 238000005476 soldering Methods 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 150000002739 metals Chemical class 0.000 claims description 15
- 230000004907 flux Effects 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 239000010949 copper Substances 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 7
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 4
- 229910020836 Sn-Ag Inorganic materials 0.000 description 3
- 229910020888 Sn-Cu Inorganic materials 0.000 description 3
- 229910020988 Sn—Ag Inorganic materials 0.000 description 3
- 229910019204 Sn—Cu Inorganic materials 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000013008 thixotropic agent Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- -1 etc. Polymers 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003685 thermal hair damage Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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
- B23K35/262—Sn as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
- B23K35/025—Pastes, creams, slurries
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
- C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
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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)
Description
本発明は、回路基板に電子部品を実装するためのはんだ合金と、これを用いたソルダペースト及び実装品に関する。 The present invention relates to a solder alloy for mounting electronic components on a circuit board, a solder paste using the same, and a mounted product.
従来、電子機器の小型化及び薄型化に伴って、モジュール化された部品の実装や、ＩＣやＬＳＩ等の半導体素子その他の各種電子部品の組立ての中で、優れた導電性と高い接合信頼性の点から、６３Ｓｎ／３７Ｐｂ（Ｓｎ／Ｐｂの質量比が６３／３７）の共晶はんだ合金が広く使用されてきた。しかし近年、環境汚染の問題から鉛に対する規制が強化され、鉛フリーはんだ合金に切り替わりつつある。 Conventionally, with the miniaturization and thinning of electronic devices, excellent electrical conductivity and high bonding reliability have been achieved in the mounting of modularized components and the assembly of various electronic components such as ICs and LSIs. From this point, eutectic solder alloys having 63Sn / 37Pb (Sn / Pb mass ratio of 63/37) have been widely used. However, in recent years, regulations on lead have been strengthened due to the problem of environmental pollution, and are switching to lead-free solder alloys.
例えば、特許文献１には、はんだ付け作業の際の有毒ガスの発生を抑制するために、燐及びゲルマニウムを含有するＳｎ−Ａｇ系はんだ合金が提案されている。特許文献２には、耐熱サイクル性を向上させるために、Ｂｉ及びＩｎの少なくとも一方を含有するＳｎ−Ｃｕ系はんだ合金が提案されている。特許文献３には、６３Ｓｎ／３７Ｐｂの共晶はんだ合金の使用温度条件に近づけるために、亜鉛を含有するＳｎ−Ａｇ系はんだ合金が提案されている。特許文献４には、はんだ付け性向上のために、燐を含有するＳｎ−Ｃｕ系はんだ合金が提案されている。
For example,
はんだ付けの際に実装品の熱損傷を防ぐには、一般的なプリント基板の耐熱温度が２５０℃以下であることを考慮すると、はんだ合金として固相線温度（示差走査熱量測定（ＤＳＣ）における融解開始温度）が２２０℃以下のものを使用することが好ましい。これにより、はんだ付け温度を低減することができる。従来の鉛フリーはんだ合金であるＳｎ−Ａｇ系合金やＳｎ−Ｃｕ系合金の固相線温度を下げるには、Ｂｉを添加すればよいが、Ｂｉを大量に添加すると、はんだが非常に脆くなるため、はんだにより接合された箇所（以下、接合箇所という）の信頼性が低下するおそれがあった。 In order to prevent thermal damage of the mounted product during soldering, considering that the heat resistance temperature of a general printed circuit board is 250 ° C. or lower, the solidus temperature (in differential scanning calorimetry (DSC)) as a solder alloy It is preferable to use one having a melting start temperature) of 220 ° C. or lower. Thereby, soldering temperature can be reduced. Bi can be added to lower the solidus temperature of conventional lead-free solder alloys such as Sn-Ag alloys and Sn-Cu alloys, but if a large amount of Bi is added, the solder becomes very brittle. For this reason, there is a possibility that the reliability of a portion joined by solder (hereinafter referred to as a joined portion) may be reduced.
本発明は、はんだ付け温度を低減できる上、接合箇所の信頼性を向上させることができる鉛フリーはんだ合金と、これを用いたソルダペースト及び実装品を提供する。 The present invention provides a lead-free solder alloy capable of reducing the soldering temperature and improving the reliability of the joint portion, and a solder paste and a mounted product using the lead-free solder alloy.
本発明者らは、特定の元素を特定の組成範囲で含有する鉛フリーはんだ合金により、はんだ付け温度を低減できる上、接合箇所の信頼性を向上できることを見出し、本発明を完成するに至った。 The present inventors have found that a lead-free solder alloy containing a specific element in a specific composition range can reduce the soldering temperature and improve the reliability of the joint location, and have completed the present invention. .
すなわち、本発明の鉛フリーはんだ合金は、Ｃｕ０．０７〜７．０質量％、Ｂｉ０．０５〜５．０質量％、Ｓｂ０．０５〜５．０質量％、Ｆｅ０．００１〜０．１質量％、Ｎｉ及びＣｏから選ばれる一種以上の金属０．０１〜１．０質量％、Ａｇ３．０質量％以下、並びに残部Ｓｎからなる鉛フリーはんだ合金であって、Ｆｅと、Ｎｉ及びＣｏから選ばれる一種以上の金属との含有量の比率（Ｆｅ／Ｎｉ及びＣｏから選ばれる一種以上の金属）が、０．００２〜５．０であることを特徴とする。 That is, the lead-free solder alloy of the present invention has Cu 0.07 to 7.0 mass%, Bi 0.05 to 5.0 mass%, Sb 0.05 to 5.0 mass%, Fe 0.001 to 0.1 mass%. A lead-free solder alloy consisting of 0.01 to 1.0% by mass of one or more metals selected from Ni and Co, Ag of 3.0% by mass or less, and the balance Sn, and selected from Fe, Ni and Co The content ratio with one or more metals (one or more metals selected from Fe / Ni and Co) is 0.002 to 5.0.
本発明のソルダペーストは、上記本発明の鉛フリーはんだ合金と、フラックスとを含有することを特徴とする。 The solder paste of the present invention contains the lead-free solder alloy of the present invention and a flux.
本発明の実装品は、電子部品と、該電子部品がはんだ付けされている回路基板とを有する実装品であって、前記はんだ付けに使用されているはんだ合金が、上記本発明の鉛フリーはんだ合金であることを特徴とする。 The mounted product of the present invention is a mounted product having an electronic component and a circuit board on which the electronic component is soldered, and the solder alloy used for the soldering is the lead-free solder of the present invention. It is an alloy.
本発明の鉛フリーはんだ合金によれば、はんだ付け温度を低減できる上、接合箇所の信頼性を向上できる。また、本発明のソルダペースト及び実装品によれば、本発明の鉛フリーはんだ合金を用いるため、はんだ付けの際の実装品の熱損傷を防ぐことができる上、接合強度やクリープ時間等を向上させることができる。 According to the lead-free solder alloy of the present invention, the soldering temperature can be reduced and the reliability of the joint location can be improved. Moreover, according to the solder paste and the mounting product of the present invention, the lead-free solder alloy of the present invention is used, so that it is possible to prevent thermal damage of the mounting product during soldering and to improve the bonding strength, the creep time, etc. Can be made.
本発明は、「鉛フリーはんだ合金」、即ち鉛が添加されていないはんだ合金を対象とする。ただし、はんだ合金中に、不可避的不純物として鉛が存在することは許容されるが、この場合、鉛の量は、１００ｐｐｍ以下であることが好ましい。以下、本発明の鉛フリーはんだ合金に含有される成分について説明する。 The present invention is directed to a “lead-free solder alloy”, ie, a solder alloy to which no lead is added. However, lead is allowed to be present as an inevitable impurity in the solder alloy, but in this case, the amount of lead is preferably 100 ppm or less. Hereinafter, the components contained in the lead-free solder alloy of the present invention will be described.
（Ｃｕ）
本発明の鉛フリーはんだ合金には、はんだによる接合強度を高めて接合箇所の信頼性を向上させるためにＣｕが含有される。Ｃｕの含有量は、接合強度向上の観点から、０．０７質量％以上であり、０．１質量％以上が好ましく、０．５質量％以上がより好ましい。また、はんだ付け温度の低減の観点から、７．０質量％以下であり、５．０質量％以下が好ましく、１．０質量％以下がより好ましい。(Cu)
The lead-free solder alloy of the present invention contains Cu in order to increase the bonding strength by the solder and improve the reliability of the bonded portion. The Cu content is 0.07% by mass or more, preferably 0.1% by mass or more, and more preferably 0.5% by mass or more, from the viewpoint of improving the bonding strength. Moreover, from a viewpoint of reduction of soldering temperature, it is 7.0 mass% or less, 5.0 mass% or less is preferable and 1.0 mass% or less is more preferable.
（Ｂｉ）
本発明の鉛フリーはんだ合金には、固相線温度を低減させるためにＢｉが含有される。Ｂｉの含有量は、固相線温度低減の観点から、０．０５質量％以上であり、０．１質量％以上が好ましく、０．５質量％以上がより好ましい。また、Ｂｉの脆性に起因する接合箇所の信頼性低下を抑制する観点から、５．０質量％以下であり、３．５質量％以下が好ましく、２．０質量％以下がより好ましい。(Bi)
The lead-free solder alloy of the present invention contains Bi in order to reduce the solidus temperature. The content of Bi is 0.05% by mass or more, preferably 0.1% by mass or more, and more preferably 0.5% by mass or more from the viewpoint of reducing the solidus temperature. Moreover, from a viewpoint of suppressing the reliability fall of the joining location resulting from the brittleness of Bi, it is 5.0 mass% or less, 3.5 mass% or less is preferable and 2.0 mass% or less is more preferable.
（Ｓｂ）
本発明の鉛フリーはんだ合金には、Ｂｉの脆性を改善することによって接合箇所の信頼性低下を抑制するためにＳｂが含有される。Ｓｂの含有量は、Ｂｉの脆性を改善する観点から０．０５質量％以上であり、０．１質量％以上が好ましく、０．３質量％以上がより好ましい。また、はんだ付け温度の低減の観点から、５．０質量％以下であり、３．５質量％以下が好ましく、２．０質量％以下がより好ましい。(Sb)
The lead-free solder alloy of the present invention contains Sb in order to improve the brittleness of Bi so as to suppress a decrease in reliability of the joint portion. The content of Sb is 0.05% by mass or more from the viewpoint of improving the brittleness of Bi, preferably 0.1% by mass or more, and more preferably 0.3% by mass or more. Moreover, from a viewpoint of reduction of soldering temperature, it is 5.0 mass% or less, 3.5 mass% or less is preferable, and 2.0 mass% or less is more preferable.
（Ｆｅ）
本発明の鉛フリーはんだ合金には、はんだによる接合強度を高め、かつ後述するクリープ時間を増大させることによって接合箇所の信頼性を向上させるために、Ｆｅが含有される。Ｆｅの含有量は、接合箇所の信頼性向上の観点から、０．００１質量％以上であり、０．００５質量％以上が好ましく、０．０１質量％以上がより好ましい。また、はんだ付け温度の低減の観点から、０．１質量％以下であり、０．０８質量％以下が好ましく、０．０５質量％以下がより好ましい。(Fe)
The lead-free solder alloy of the present invention contains Fe in order to increase the bonding strength by the solder and to improve the reliability of the bonded portion by increasing the creep time described later. The content of Fe is 0.001% by mass or more, preferably 0.005% by mass or more, and more preferably 0.01% by mass or more from the viewpoint of improving the reliability of the joint. Moreover, from a viewpoint of reduction of soldering temperature, it is 0.1 mass% or less, 0.08 mass% or less is preferable and 0.05 mass% or less is more preferable.
（Ｎｉ及びＣｏから選ばれる一種以上の金属）
本発明の鉛フリーはんだ合金には、はんだによる接合強度を高め、かつ後述するクリープ時間を増大させることによって接合箇所の信頼性を向上させるために、Ｎｉ及びＣｏから選ばれる一種以上の金属が含まれ、接合箇所の信頼性向上の観点から好ましくはＣｏが含まれる。Ｎｉ及びＣｏから選ばれる一種以上の金属の合計含有量は、接合箇所の信頼性向上の観点から、０．０１質量％以上であり、０．０５質量％以上が好ましく、０．１質量％以上がより好ましい。また、はんだ付け温度の低減の観点から、１．０質量％以下であり、０．５質量％以下が好ましく、０．３質量％以下がより好ましい。(One or more metals selected from Ni and Co)
The lead-free solder alloy of the present invention contains one or more metals selected from Ni and Co in order to increase the joint strength by soldering and improve the reliability of the joint location by increasing the creep time described later. From the viewpoint of improving the reliability of the joint portion, Co is preferably included. The total content of one or more metals selected from Ni and Co is 0.01% by mass or more, preferably 0.05% by mass or more, and preferably 0.1% by mass or more, from the viewpoint of improving the reliability of the joint portion. Is more preferable. Moreover, from a viewpoint of reduction of soldering temperature, it is 1.0 mass% or less, 0.5 mass% or less is preferable and 0.3 mass% or less is more preferable.
本発明の鉛フリーはんだ合金において、はんだによる接合強度を高め、かつ後述するクリープ時間を増大させることによって接合箇所の信頼性を向上させる観点から、Ｆｅと、Ｎｉ及びＣｏから選ばれる一種以上の金属との含有量の比率（Ｆｅ／Ｎｉ及びＣｏから選ばれる一種以上の金属）は、０．００２〜５．０であり、０．０１〜３．０であることが好ましく、０．０５〜０．５であることがより好ましい。 In the lead-free solder alloy of the present invention, one or more metals selected from Fe, Ni, and Co are used from the viewpoint of improving the bonding strength by soldering and improving the reliability of the bonded portion by increasing the creep time described later. The content ratio (one or more metals selected from Fe / Ni and Co) is 0.002 to 5.0, preferably 0.01 to 3.0, and 0.05 to 0. .5 is more preferable.
（Ａｇ）
本発明の鉛フリーはんだ合金には、はんだによる接合強度を高める観点から、Ａｇが含有されていることが好ましい。Ａｇの含有量は、接合強度向上の観点から、０．１質量％以上が好ましく、０．３質量％以上がより好ましく、０．５質量％以上が更に好ましい。また、はんだ付け温度の低減及びコスト低減の観点から、３．０質量％以下であり、２．０質量％以下が好ましく、１．０質量％以下がより好ましい。(Ag)
The lead-free solder alloy of the present invention preferably contains Ag from the viewpoint of increasing the bonding strength by solder. The content of Ag is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.5% by mass or more from the viewpoint of improving the bonding strength. Moreover, from a viewpoint of reduction of soldering temperature and cost reduction, it is 3.0 mass% or less, 2.0 mass% or less is preferable and 1.0 mass% or less is more preferable.
（Ｓｎ及びその他の成分）
本発明の鉛フリーはんだ合金は、上述した各元素が上記特定の組成範囲で含有され、その残部がＳｎである。ただし、はんだ合金中に、不可避的不純物として上述した各元素及びＳｎ以外の他の成分が存在することは許容されるが、この場合、他の成分の量は、１００ｐｐｍ以下であることが好ましい。Ｓｎの含有量は、接合箇所の信頼性向上の観点から、８０．５〜９９．８質量％であることが好ましく、８７．０〜９９．５質量％であることがより好ましく、９４．５〜９８．５質量％であることが更に好ましい。(Sn and other ingredients)
In the lead-free solder alloy of the present invention, each of the elements described above is contained in the specific composition range, and the balance is Sn. However, although it is allowed that other components other than the above-described elements and Sn as inevitable impurities are present in the solder alloy, in this case, the amount of the other components is preferably 100 ppm or less. The content of Sn is preferably 80.5 to 99.8% by mass, more preferably 87.0 to 99.5% by mass, from the viewpoint of improving the reliability of the joint portion, and 94.5 More preferably, it is ˜98.5 mass%.
本発明の鉛フリーはんだ合金は、はんだ付け温度の低減の観点から、その固相線温度が２２０℃以下であることが好ましく、２１７℃以下であることがより好ましく、２１４℃以下であることが更に好ましい。固相線温度を上記範囲に制御するには、例えばＢｉの含有量を調整すればよい。 The lead-free solder alloy of the present invention has a solidus temperature of preferably 220 ° C. or lower, more preferably 217 ° C. or lower, and 214 ° C. or lower, from the viewpoint of reducing the soldering temperature. Further preferred. In order to control the solidus temperature within the above range, for example, the Bi content may be adjusted.
本発明の鉛フリーはんだ合金は、粉末形状であることが好ましい。後述するフラックスへの分散性が向上するからである。 The lead-free solder alloy of the present invention is preferably in a powder form. This is because dispersibility in the flux described later is improved.
次に、本発明のソルダペーストについて説明する。本発明のソルダペーストは、上述した本発明の鉛フリーはんだ合金と、フラックスとを含有する。フラックスとしては、特に限定されず、従来のソルダペーストで使用されている配合のものを使用できる。例えば、ロジン系樹脂、活性剤、チクソ剤、溶剤等を含有するロジン系樹脂含有フラックスや、熱硬化性樹脂、活性剤、チクソ剤、硬化剤等を含有する熱硬化性樹脂含有フラックス等が使用できる。なかでも、はんだ付け時の作業性及びリペアの容易性の観点から、ロジン系樹脂含有フラックスを使用するのが好ましい。 Next, the solder paste of the present invention will be described. The solder paste of the present invention contains the above-described lead-free solder alloy of the present invention and a flux. It does not specifically limit as a flux, The thing of the mixing | blending used with the conventional solder paste can be used. For example, rosin resin-containing flux containing rosin resin, activator, thixotropic agent, solvent, etc., thermosetting resin-containing flux containing thermosetting resin, activator, thixotropic agent, curing agent, etc. are used it can. Especially, it is preferable to use a rosin-based resin-containing flux from the viewpoint of workability during soldering and ease of repair.
本発明のソルダペーストにおいて、フラックスの含有量は、９〜１３質量％であることが好ましく、１０〜１２質量％であることがより好ましい。上記範囲とすることにより、ペーストとしての粘性やチクソ性が良好となり、印刷やディスペンス塗布などの量産工程に適したソルダペーストが得られる。同様の観点から、本発明のソルダペーストにおいて、鉛フリーはんだ合金の含有量は、８１〜９１質量％であることが好ましく、８８〜９０質量％であることがより好ましい。 In the solder paste of the present invention, the flux content is preferably 9 to 13% by mass, and more preferably 10 to 12% by mass. By setting it as the said range, the viscosity and thixotropy as a paste will become favorable, and the solder paste suitable for mass production processes, such as printing and dispensing application | coating, will be obtained. From the same viewpoint, in the solder paste of the present invention, the content of the lead-free solder alloy is preferably 81 to 91% by mass, and more preferably 88 to 90% by mass.
本発明のソルダペースト、又はソルダペーストに含まれるフラックスは、上述した成分に加えて、必要に応じて種々の添加剤、例えば界面活性剤、消泡剤、レベリング剤等の添加剤などを含有することができる。なかでも、界面活性剤を添加すると、はんだ濡れ広がり性が向上するため好ましい。 The solder paste of the present invention or the flux contained in the solder paste contains various additives as necessary, for example, additives such as surfactants, antifoaming agents, leveling agents, etc. in addition to the above-described components. be able to. Among these, it is preferable to add a surfactant because solder wettability is improved.
本発明のソルダペーストは、接合箇所の信頼性向上の観点から、後述する実施例に記載の測定方法により測定した接合強度が７０ＭＰａ以上であることが好ましく、８０ＭＰａ以上であることがより好ましく、９０ＭＰａ以上であることが更に好ましい。なお、上記接合強度は、通常１ＧＰａ以下である。接合強度を上記範囲内に制御するには、例えば、Ｆｅ、Ｎｉ、Ｃｏ等の含有量や、Ｆｅと、Ｎｉ及びＣｏから選ばれる一種以上の金属との含有量の比率（Ｆｅ／Ｎｉ及びＣｏから選ばれる一種以上の金属）を調整すればよい。 The solder paste of the present invention preferably has a bonding strength of 70 MPa or more, more preferably 80 MPa or more, more preferably 90 MPa, from the viewpoint of improving the reliability of the joint location, as measured by the measurement method described in the examples described later. It is still more preferable that it is above. The bonding strength is usually 1 GPa or less. In order to control the bonding strength within the above range, for example, the content of Fe, Ni, Co or the like, or the ratio of the content of Fe and one or more metals selected from Ni and Co (Fe / Ni and Co) One or more metals selected from the above may be adjusted.
本発明のソルダペーストは、接合箇所の熱的疲労による信頼性低下を抑制する観点から、後述する実施例に記載の測定方法により測定したクリープ時間が１６０時間以上であることが好ましく、１７０時間以上であることがより好ましく、１８０時間以上であることが更に好ましい。なお、上記クリープ時間は、通常１０００時間以下である。クリープ時間を上記範囲内に制御するには、例えば、Ｆｅ、Ｎｉ、Ｃｏ等の含有量や、Ｆｅと、Ｎｉ及びＣｏから選ばれる一種以上の金属との含有量の比率（Ｆｅ／Ｎｉ及びＣｏから選ばれる一種以上の金属）を調整すればよい。 The solder paste of the present invention preferably has a creep time of 160 hours or more, measured by the measurement method described in the examples described later, from the viewpoint of suppressing reliability deterioration due to thermal fatigue at the joints, and 170 hours or more. It is more preferable that it is 180 hours or more. The creep time is usually 1000 hours or less. In order to control the creep time within the above range, for example, the content of Fe, Ni, Co or the like, or the ratio of the content of Fe and one or more metals selected from Ni and Co (Fe / Ni and Co) One or more metals selected from the above may be adjusted.
本発明のソルダペーストは、上述した必須成分及び必要に応じて添加される添加剤と共に混練処理することにより容易に製造することができる。 The solder paste of the present invention can be easily produced by kneading together with the above-described essential components and additives added as necessary.
次に、本発明の実装品について説明する。本発明の実装品は、電子部品と回路基板とを有し、前記電子部品と前記回路基板とを接合するはんだ合金として、上述した本発明の鉛フリーはんだ合金が使用されている。例えば、前記電子部品と前記回路基板とが、上述した本発明のソルダペーストを用いてはんだ付けされた実装品が例示できる。なお、電子部品は特に限定されず、例えば太陽光発電モジュール等が使用できる。また、回路基板についても特に限定されず、例えばポリイミド等を基材の材料とする回路基板が使用できる。 Next, the mounted product of the present invention will be described. The mounted product of the present invention has an electronic component and a circuit board, and the above-described lead-free solder alloy of the present invention is used as a solder alloy for joining the electronic component and the circuit board. For example, a mounted product in which the electronic component and the circuit board are soldered using the solder paste of the present invention described above can be exemplified. In addition, an electronic component is not specifically limited, For example, a solar power generation module etc. can be used. Further, the circuit board is not particularly limited, and for example, a circuit board using polyimide or the like as a base material can be used.
以下に実施例を示し、本発明をより具体的に説明する。これら実施例は、本発明における最良の実施形態の一例ではあるものの、本発明はこれら実施例により限定を受けるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. These examples are examples of the best mode of the present invention, but the present invention is not limited by these examples.
（鉛フリーはんだ合金粉末の作製及び固相線温度測定）
表１に示す各組成のはんだ合金を作製し、次いでそれらを粉末化し、粒径２０μｍから４０μｍの間にあるものを分級し、評価に使用する鉛フリーはんだ合金粉末を得た。得られた各鉛フリーはんだ合金粉末について、示差走査熱量計（セイコーインスツルメント社製、ＥＸＳＴＡＲ６０００）を用い、測定温度範囲を３０〜６００℃として、固相線温度を測定した。結果を表１に示す。なお、測定の際は、吸熱量が１．５Ｊ／ｇ以上あるものを測定対象物由来のピークとし、それ未満のピークは、分析精度の観点から除外した。(Preparation of lead-free solder alloy powder and measurement of solidus temperature)
Solder alloys having respective compositions shown in Table 1 were prepared, and then pulverized, and those having a particle size between 20 μm and 40 μm were classified to obtain lead-free solder alloy powders used for evaluation. About each obtained lead-free solder alloy powder, the solidus line temperature was measured by using a differential scanning calorimeter (manufactured by Seiko Instruments Inc., EXSTAR6000) with a measurement temperature range of 30 to 600 ° C. The results are shown in Table 1. In the measurement, those having an endothermic amount of 1.5 J / g or more were regarded as peaks derived from the measurement object, and peaks less than that were excluded from the viewpoint of analysis accuracy.
（ソルダペーストの調製）
ロジン系樹脂（ハリマ化成社製 ハリフェノール５１２）４８質量％、チクソ剤（新日本理化社製 ゲルオールＤ）９質量％、活性剤（アジピン酸）８質量％、界面活性剤（ビックケミージャパン社製 ＢＹＫ３６１Ｎ）１質量％、及び溶剤としてヘキシルジグリコール３４質量％を同容器に計量し、らいかい機を用いて混合し、フラックスを調製した。得られたフラックスと、上記の方法で得られた各鉛フリーはんだ合金粉末とを、フラックス：はんだ粉末＝１０：９０の比率で計量し、これらを混練機にて２時間混合することで、ソルダペーストを調製した。このソルダペーストを用いて、後述する各種物性評価を行った。(Preparation of solder paste)
Rosin resin (Harima Chemical Co., Ltd., Hariphenol 512) 48% by mass, thixotropic agent (Shin Nippon Rika Co., Ltd., Gelol D) 9% by mass, activator (adipic acid) 8% by mass, surfactant (Bic Chemie Japan, Inc.) BYK361N) 1% by mass and 34% by mass of hexyl diglycol as a solvent were weighed in the same container and mixed using a rough machine to prepare a flux. Solder was obtained by weighing the obtained flux and each lead-free solder alloy powder obtained by the above method in a ratio of flux: solder powder = 10: 90, and mixing them in a kneader for 2 hours. A paste was prepared. Using this solder paste, various physical property evaluations described later were performed.
（接合強度の測定）
接合強度の測定方法について、図１を参照しながら説明する。図１は、接合強度の測定方法を説明するための平面図である。まず、銅板１（５ｍｍ×５０ｍｍ、厚さ０．５ｍｍ）を２枚準備し、２枚の銅板１の短辺部同士を合わせ、その間に上記の方法で得られた各ソルダペースト２（１ｍｍ×５ｍｍ、厚さ０．５ｍｍ）を挟み、図２に示すリフロー条件にてリフロー溶融させることによって、２枚の銅板１同士を接合させた。得られた試料を、引張り試験機（ＳＨＩＭＡＤＺＵ社製、ＥＺ−Ｌ）を使用して、引っ張り速度５ｍｍ／ｍｉｎの条件で図１に示す矢印方向に引っ張って、接合強度（接合箇所が破断する強度）を測定した。結果を表１に示す。(Measurement of bonding strength)
A method for measuring the bonding strength will be described with reference to FIG. FIG. 1 is a plan view for explaining a method for measuring the bonding strength. First, two copper plates 1 (5 mm × 50 mm, thickness 0.5 mm) were prepared, the short sides of the two
（クリープ時間の測定）
クリープ時間の測定方法について、図３を参照しながら説明する。図３は、クリープ時間の測定方法を説明するための断面図である。まず、ガラスエポキシ基板３上に銅ランド４（径４．０ｍｍ）が設けられた試験基板を準備し、ガラスエポキシ基板３及び銅ランド４を貫通する貫通孔５（孔径１．０ｍｍ）を設けた。別途、上記の方法で得られた各ソルダペーストを用いて６．０ｍｍ径の円形はんだ６（重量２ｇ、中心に直径１．０ｍｍの孔６ａが設けられたもの）をそれぞれ作製した。次いで、貫通孔５に０．８ｍｍ径の銅線７を通し、更に銅線７の上部を円形はんだ６の孔６ａに通した状態で、図２に示すリフロー条件にてリフロー溶融させることによって、銅ランド４と銅線７とを固定した。次いで、銅線７の下部に錘８（重量２ｋｇ）を吊るし、１２５℃の恒温槽内に放置し、放置直後から錘８が落下するまでの時間をクリープ時間として記録した。結果を表１に示す。なお、クリープ時間が長いほど、接合箇所の熱的疲労による信頼性低下を抑制できる。(Measurement of creep time)
A method for measuring the creep time will be described with reference to FIG. FIG. 3 is a cross-sectional view for explaining a creep time measurement method. First, a test board provided with a copper land 4 (diameter 4.0 mm) on a
（せん断強度の測定）
ガラスエポキシ基板上に形成された銅箔ランド（導体寸法：０．８５×０．５５ｍｍ、導体間隔：０．８５ｍｍ）に、上記の方法で得られた各ソルダペーストを、厚み１５０μｍｔのメタルマスクを用いてメタルスキージで印刷した。次いで、Ｓｎめっきされた１６０８ＣＲチップを上記銅箔ランド（１０個）の印刷膜上に１つずつ載置した。そして、図２に示すリフロー条件で加熱して試験片を作製した。この試験片について、引張り試験機（ＳＨＩＭＡＤＺＵ社製、ＥＺ−Ｌ）を用いて、引っ張り速度５ｍｍ／ｍｉｎの条件でチップのせん断強度を測定した。結果を表１に示す。なお、表１の結果は、せん断強度を測定した１０個のチップの平均値である。(Measurement of shear strength)
Copper solder lands (conductor dimensions: 0.85 x 0.55 mm, conductor spacing: 0.85 mm) formed on a glass epoxy substrate are coated with each solder paste obtained by the above method using a metal mask with a thickness of 150 μmt. Used to print with a metal squeegee. Next, 1608CR chips plated with Sn were placed one by one on the printed film of the copper foil lands (10 pieces). And it heated on the reflow conditions shown in FIG. 2, and produced the test piece. About this test piece, the shear strength of the chip | tip was measured on the conditions of the tension | pulling speed of 5 mm / min using the tensile tester (the product made by SHIMADZU, EZ-L). The results are shown in Table 1. In addition, the result of Table 1 is an average value of 10 chips | tips which measured shear strength.
表１に示すように、本発明の実施例１〜１２は、いずれの評価項目についても良好な結果が得られた。一方、比較例１〜１１は、少なくとも１つの評価項目について実施例よりも劣る結果が得られた。 As shown in Table 1, in Examples 1 to 12 of the present invention, good results were obtained for any of the evaluation items. On the other hand, in Comparative Examples 1 to 11, results inferior to those of the Examples were obtained for at least one evaluation item.
１ 銅板
２ ソルダペースト
３ ガラスエポキシ基板
４ 銅ランド
５ 貫通孔
６ 円形はんだ
６ａ 孔
７ 銅線
８ 錘DESCRIPTION OF
Claims (8)
Ｆｅと、Ｎｉ及びＣｏから選ばれる一種以上の金属との含有量の比率（Ｆｅ／Ｎｉ及びＣｏから選ばれる一種以上の金属）が、０．００７〜５．０である、鉛フリーはんだ合金。
Cu 0.1-5.0 % by mass, Bi 0.1-3.5 % by mass, Sb 0.1-3.5 % by mass, Fe 0.001-0.1 % by mass, a kind selected from Ni and Co A lead-free solder alloy comprising the above metals 0.01 to 0.5 % by mass, Ag 3.0% by mass or less, and the balance Sn,
A lead-free solder alloy in which the content ratio of Fe to one or more metals selected from Ni and Co (one or more metals selected from Fe / Ni and Co) is 0.007 to 5.0.
前記はんだ付けに使用されているはんだ合金が、請求項１〜３の何れか１項記載の鉛フリーはんだ合金である実装品。A mounted product having an electronic component and a circuit board to which the electronic component is soldered,
The mounted product in which the solder alloy used for the soldering is the lead-free solder alloy according to any one of claims 1 to 3.
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| PCT/JP2010/070451 WO2011102034A1 (en) | 2010-02-16 | 2010-11-17 | Lead-free solder alloy, and solder paste and packaged components using same |
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| WO2014002304A1 (en) * | 2012-06-29 | 2014-01-03 | ハリマ化成株式会社 | Solder alloy, solder paste, and electronic circuit board |
| JP5238088B1 (en) | 2012-06-29 | 2013-07-17 | ハリマ化成株式会社 | Solder alloy, solder paste and electronic circuit board |
| WO2014013632A1 (en) * | 2012-07-19 | 2014-01-23 | ハリマ化成株式会社 | Solder alloy, solder paste, and electronic circuit board |
| JP5723056B1 (en) * | 2014-12-15 | 2015-05-27 | ハリマ化成株式会社 | Solder alloy, solder paste and electronic circuit board |
| JP6200534B2 (en) * | 2015-03-24 | 2017-09-20 | 株式会社タムラ製作所 | Lead-free solder alloy, electronic circuit board and electronic control device |
| JP6011709B1 (en) * | 2015-11-30 | 2016-10-19 | 千住金属工業株式会社 | Solder alloy |
| JP2016107343A (en) * | 2015-12-24 | 2016-06-20 | 千住金属工業株式会社 | Lead-free solder alloy, and on-vehicle electronic circuit |
| JP6052381B2 (en) * | 2015-12-24 | 2016-12-27 | 千住金属工業株式会社 | Lead-free solder alloy |
| MX2018011176A (en) | 2016-03-22 | 2019-03-28 | Tamura Seisakusho Kk | Lead-free solder alloy, flux composition, solder paste composition, electronic circuit board and electronic control device. |
| US10456872B2 (en) | 2017-09-08 | 2019-10-29 | Tamura Corporation | Lead-free solder alloy, electronic circuit substrate, and electronic device |
| US11577343B2 (en) * | 2017-11-09 | 2023-02-14 | Alpha Assembly Solutions Inc. | Low-silver alternative to standard SAC alloys for high reliability applications |
| EP4086031A1 (en) * | 2021-05-05 | 2022-11-09 | Heraeus Deutschland GmbH & Co. KG | Alloy |
| JP7323854B1 (en) | 2023-01-12 | 2023-08-09 | 千住金属工業株式会社 | Solder alloys, solder pastes, solder balls, solder preforms, solder joints, automotive electronic circuits, ECU electronic circuits, automotive electronic circuit devices, and ECU electronic circuit devices |
| JP7323853B1 (en) | 2023-01-12 | 2023-08-09 | 千住金属工業株式会社 | Solder alloys, solder pastes, solder balls, solder preforms, solder joints, automotive electronic circuits, ECU electronic circuits, automotive electronic circuit devices, and ECU electronic circuit devices |
| JP7323855B1 (en) | 2023-01-12 | 2023-08-09 | 千住金属工業株式会社 | Solder alloys, solder pastes, solder balls, solder preforms, solder joints, automotive electronic circuits, ECU electronic circuits, automotive electronic circuit devices, and ECU electronic circuit devices |
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|---|---|---|---|---|
| JP2000288772A (en) * | 1999-02-02 | 2000-10-17 | Nippon Genma:Kk | Lead-free solder |
| JP2002086294A (en) * | 2000-09-14 | 2002-03-26 | Nippon Steel Corp | Electronic member having solder alloy, solder ball and solder bump |
| JP2002239780A (en) * | 2001-02-09 | 2002-08-28 | Nippon Steel Corp | Electronic member having solder alloy, solder ball and solder bump |
| JP2004261863A (en) * | 2003-01-07 | 2004-09-24 | Senju Metal Ind Co Ltd | Lead-free solder |
| JP2005118800A (en) * | 2003-10-15 | 2005-05-12 | Senju Metal Ind Co Ltd | High-temperature lead-free solder for lamp |
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- 2010-11-17 WO PCT/JP2010/070451 patent/WO2011102034A1/en active Application Filing
- 2010-11-17 JP JP2012500457A patent/JP5722302B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000288772A (en) * | 1999-02-02 | 2000-10-17 | Nippon Genma:Kk | Lead-free solder |
| JP2002086294A (en) * | 2000-09-14 | 2002-03-26 | Nippon Steel Corp | Electronic member having solder alloy, solder ball and solder bump |
| JP2002239780A (en) * | 2001-02-09 | 2002-08-28 | Nippon Steel Corp | Electronic member having solder alloy, solder ball and solder bump |
| JP2004261863A (en) * | 2003-01-07 | 2004-09-24 | Senju Metal Ind Co Ltd | Lead-free solder |
| JP2005118800A (en) * | 2003-10-15 | 2005-05-12 | Senju Metal Ind Co Ltd | High-temperature lead-free solder for lamp |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160056570A1 (en) * | 2013-04-02 | 2016-02-25 | Senju Metal Industry Co., Ltd. | Lead-free solder alloy and in-vehicle electronic circuit |
| US9837757B2 (en) * | 2013-04-02 | 2017-12-05 | Senju Metal Industry Co., Ltd. | Lead-free solder alloy and in-vehicle electronic circuit |
| US11732330B2 (en) | 2017-11-09 | 2023-08-22 | Alpha Assembly Solutions, Inc. | High reliability lead-free solder alloy for electronic applications in extreme environments |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2011102034A1 (en) | 2011-08-25 |
| JPWO2011102034A1 (en) | 2013-06-17 |
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