WO2003061897A1 - Materiau de soudage sans plomb - Google Patents

Materiau de soudage sans plomb Download PDF

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Publication number
WO2003061897A1
WO2003061897A1 PCT/JP2003/000470 JP0300470W WO03061897A1 WO 2003061897 A1 WO2003061897 A1 WO 2003061897A1 JP 0300470 W JP0300470 W JP 0300470W WO 03061897 A1 WO03061897 A1 WO 03061897A1
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WO
WIPO (PCT)
Prior art keywords
alloy
lead
free solder
fine
primary
Prior art date
Application number
PCT/JP2003/000470
Other languages
English (en)
Japanese (ja)
Inventor
Toshio Narita
Junichi Tanaka
Taiki Kobayashi
Original Assignee
Japan Science And Technology Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Japan Science And Technology Corporation filed Critical Japan Science And Technology Corporation
Publication of WO2003061897A1 publication Critical patent/WO2003061897A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/264—Bi as the principal constituent

Definitions

  • the present invention relates to a soft solder material, a so-called solder material, which is used for circuit connection of electric / electronic components and joining of metal members in the electronics industry, and more particularly to a so-called lead-free solder material from which lead is eliminated.
  • Solder materials are widely used as electrical connection and mechanical fixing means, starting with the mounting and fixing of electronic components in the electronics industry. Sn-Pb, which has been conventionally used as solder, is widely used. Due to the lead contained in these alloys, toxicity is an issue in the disposal and recovery of used products as well as in the working environment.In recent years, to reduce or eliminate the burden on these environments, they have been used as alternative materials. The development of so-called lead-free solder materials that do not contain lead is underway.
  • solder materials are required not to cause thermal damage to the target electronic components and resist materials during electronics mounting, or to cause distortion of resin-containing substrates and the like. —Similar to Pb solder, low melting point, strength of connection / fixed part, reliability, etc. are required. In particular, in recent electronic packaging, these requirements are becoming more stringent as the miniaturization of components and the like and the development of high-density surface mounting are advanced.
  • new lead-free solder materials are based on eutectic alloys containing Sn as the main component, Ag and other components, with the aim of lowering the melting point and refining the crystal structure to meet these conditions.
  • the composition is selected.
  • solder materials Sn-Ag eutectic, and those added with Cu, Bi, and In individually or in combination to lower the melting point and improve mechanical properties, etc. Reported in each country. (See JP-A-2000-94181, JP-A-7-51883, etc.)
  • Sn-based solder alloys are generally applied to soldering in the mounting of electronic components, the actually formed metal structure is unlikely to have a fine eutectic structure despite the eutectic composition.
  • the problem is that the primary ⁇ -Sn phase develops and forms a two-phase mixed structure consisting of this and the eutectic phase, resulting in a decrease in mechanical properties such as material strength.
  • the Sn-3.OAg-O.5Cu alloy, etc. which has been put into practical use as a promising alternative solder material, has a high content of expensive Ag and significant cost cost. Since it is unavoidable that the eutectic composition becomes high, the reduction of the Ag content is desired.If these compositions are changed and deviated from the initial eutectic composition, the intended fine eutectic structure cannot be obtained, The mechanical properties of cannot be obtained.
  • solder alloy materials are heated by the flow method and the reflow method, including the mounted electronic components and substrates, and then cooled by cooling.
  • the melting and solidification of the solder material progresses.However, the cooling rate differs significantly depending on the type and process of the mounted component. Since the obtained metallographic structure is not always a homogeneous and uniform structure, the quality is not stable.
  • the present invention relates to a Sn-based lead-free solder material
  • the present invention provides a Sn-Ag binary alloy, addition of AI, Te cowpea coagulation with heterogeneous nucleation, a lead-free solder material of the material structure is miniaturized, further 0.1wto the Ag / o It is a lead-free solder alloy that contains 0.1 to 5 wt% of AI in an alloy containing 5 to 5 wt%, Gu: 0.1 to 3.0 wt%, and the balance Sn.
  • Bi 40 to 60 wto / o or In: 40 to 50 wt ⁇ 1 ⁇ 2 is contained, or in the above composition, Cu: 0.1 to 5 wto / o, and further, In, Bi, Ni, Au Lead containing 0.1 to 5 wt% of one or more elements selected from the group consisting of, Sb, Zn, Mg, La, and Ce Free solder material.
  • FIG. 1 is an enlarged microstructure of a solder alloy of the present invention (A) and a comparative alloy (B) based on micrographs
  • FIG. 2 is a cooling rate and a crystal of the solder alloy of the present invention and a comparative alloy.
  • FIG. 3 is an explanatory diagram showing the relationship between the particle sizes
  • FIG. 3 is a concentration distribution diagram of each contained element in the solder alloy of the present invention.
  • the alloy composition of the present invention is in a range where a coarse primary crystal ⁇ -Sn phase is crystallized, the cooling rate is not affected by the addition of a small amount of AI, and the cooling rate under solder mounting conditions is not affected. In addition, finer metal structures can be achieved.
  • the present inventors have found that despite the fact that these Sn-based solder alloys have a eutectic structure, the material structure is not refined under the mounting conditions, and a coarse primary crystal) 6-Sn phase is formed. Considering the cause of crystallization, these alloys differ from the solidification process under equilibrium conditions, and when given a certain cooling rate, the eutectic composition shifts to the higher Ag side, and the actual solidification structure changes to the eutectic composition. We noticed that it should not be.
  • the eutectic crystal of the primary crystal -Sn phase, / S -Sn phase, and Ag 3 Sn intermetallic compound crystallizes out and crystallizes in the primary crystal.
  • 8 -Sn phase is softer than the eutectic phase. However, the material strength was reduced due to the large particle size.
  • the material strength improves when the ⁇ -Sn phase crystallized in the primary crystal is refined and a uniform structure is obtained, but the structure of the conventional Sn-Ag-based alloy is controlled by controlling the eutectic composition region. Since it is difficult to make the entire surface a eutectic phase, the present inventors have conceived of forming heterogeneous nuclei in the molten metal and simultaneously crystallizing the crystals during the solidification process.
  • Al 2 0 3 from the function as generally potent heterogeneous nucleation is known, and discussed how to function as Oite heterogeneous nuclei Sn-based alloy.
  • Al 2 0 3 acts as a potent heterogeneous nucleation relative sn.
  • a latent heat phenomenon (a step due to) appears in the cooling curve due to homogeneous nucleation with large supercooling, whereas the Sn-Ag alloy
  • supercooling was suppressed, and the crystallization transformation point of the primary crystal did not appear. From this, it was understood that it functioned as a heterogeneous nucleus of AI force and nucleation was performed simultaneously and frequently.
  • the Sn-A alloy does not have a heterogeneous nuclear force during solidification, it is characterized by a large supercooling force.Therefore, in actual soldering operations, the cooling rate at which the solder solidifies depends on the conditions of each condition. When it is below, the composition shifts from the composition shown in the equilibrium diagram to the high alloy side, showing a hypoeutectic structure even with the eutectic composition, and the primary crystal jS-Sn phase with a large grain size and fine eutectic It is a mixed organization with.
  • the material structure can be refined under a wide cooling rate condition in the mounting conditions, and the Ag content can be reduced without lowering its mechanical properties.
  • the present invention it is achieved by setting the Ag content in the range of 0.1 wt% to 5 wt% and the Al content in the range of 0.1 wt% to 5.0 wto / 0 with Sn as the basic composition.
  • the minimum content of 0.1 wt% is the minimum condition for maintaining the strength of the solder material, and the maximum content of 5 wto / 0 is based on the hypoeutectic composition when the cooling rate is accelerated during mounting. This is the boundary composition in the range that transforms to the eutectic composition.
  • the minimum content of 0.1 wt ⁇ 1 ⁇ 2 is the minimum condition for adding Cu, that is, improving wettability and maintaining the material strength, and the maximum content of 3.0 wt% maintains the material strength while maintaining the melting temperature. This is the limit area where rapid rise can be suppressed.
  • the minimum content of 40wt ⁇ 1 ⁇ 2 is the limit concentration at which eutectic crystallizes out of 43wt ⁇ to reduce the strength of the material, and 50wt ⁇ 1 ⁇ 2 is the limit point for suppressing the sharp rise in melting point.
  • the minimum content of 40 wt% is the minimum condition that changes the phase structure, and 50 wt% is the minimum limit composition that suppresses the rise in melting point.
  • each of the additional elements of claim 4 has a role of improving the effect of lowering the melting point and improving the wettability.
  • Bi, Sb, and Zn are elements that lower the melting point. No effect can be obtained if the content is less than 0.1 wt ⁇ 1 ⁇ 2, and a remarkable effect cannot be expected if the concentration is less than 5 wt%. In addition, the addition of 5 wto / 0 or more results in poor wettability.
  • Ni, Cu, and Au are mixed in the molten metal during mounting because they are used as electronic component substrate materials during mounting.
  • the effect of these elements is to improve wettability.
  • the minimum content of 0.1 wt% is the minimum condition that the effect can be exhibited, and 5 wt ⁇ 1 ⁇ 2 is the limit concentration at which the effect continues. Addition of more than 5 wt% adversely affects wettability and lowers material strength.
  • Mg, La, and Ce are added as elements that strengthen the grain boundary spaces in the material structure and increase the material strength. Therefore, the minimum concentration of 0.1 wt% is the lowest content that can exhibit the effect, and 5 wt% is the limit concentration that can exhibit the effect.
  • FIGS. 1 (a), (b) and (c) show the structures (b) and (c) (photographs) of the example (a) and the comparative example solidified at the above cooling rate of 10 KZs.
  • the eutectic structure of the 8-Sn phase and the Ag 3 Sn phase was densely formed in the gap between the primary ⁇ -Sn phases. From this result, it is found that the ⁇ -Sn phase and the eutectic phase do not have a fixed area in each other. It became clear that the structure was formed with a reinforced distribution. This has great significance for improving the material strength.
  • FIG. 2 shows the relationship between the grain size of the primary ⁇ 1 Sn phase and the cooling rate of the alloys of the present invention and the comparative example.
  • Fig. 3 shows the results of measuring the concentration distribution in the structure of the alloy of the present invention in which AIO. 1 wt% was added to a hypoeutectic alloy of Sn-2. Owt% Ag.
  • the main figure in this figure can grasp the particle size of the primary ⁇ -Sn phase and the particle size and phase structure of the intermetallic compound present in the intergranular gap.
  • Ag and AI concentrations increase where Sn concentration changes from the Ag and AI concentration distributions.
  • the changes in the concentrations of Ag and AI show the same transition.
  • phase existing in the intergranular gap is an intermetallic compound different from the primary ⁇ -Sn phase. Because Ag and AI do not dissolve in the primary ⁇ -Sn phase, the above facts can be understood.
  • AI when AI is added to Sn-Ag alloy, AI has no solubility in Sn. It can be inferred to be changed to 2 0 3.
  • Alloys of the present invention the Sn-based solder alloy, the tissue by crystallizing the multiple simultaneous manner crystals formed and solidification process a heterogeneous nuclei by Ri during the melt in Al 2 0 3 which is formed by AI added Since it is miniaturized, its effect can be exerted in a wide range from the hypoeutectic composition to the Ag content with respect to Sn to the hypereutectic composition.
  • solder alloys containing elements such as Mg, La, and Ce by the same mechanism. It is possible to suppress the coarsening of the 8-—Sn phase and achieve the refinement of the microstructure. in solder alloys containing one or more of these elements, if component range, the availability of the c industry can exert the effects of the present invention together with the characteristics improvement by these containing component
  • the lead-free solder alloy material of the present invention improves the mechanical properties of the conventional Sn-Ag binary lead-free solder material and reduces the difference in solder cooling rate. Because without being affected can exhibit an improvement in refining 'mechanical properties of the material structure, high density, suitable for significant electronics soldering miniaturization of components, also an expensive A g content Because it can be reduced, it will promote its spread through cost reduction and contribute to the development of these industries.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

L'invention concerne un matériau de soudage sans plomb, constitué d'un alliage binaire Sn-Ag incorporant de l'aluminium et présentant ainsi une fine structure induite, à travers de nombreuses formations cristallines simultanées, par une coagulation accompagnée d'une nucléation hétérogène. Dans un premier mode de réalisation, le matériau comprend de 0,1 à 5 % en poids de Ag et est incorporé dans un alliage contenant de 0,1 à 5 % en poids de Al et une quantité d'équilibre de Sn. Dans un deuxième mode de réalisation, le matériau contient également de 0,1 à 3 % en poids de Cu, et de 40 à 60 % en poids de Bi ou de 40 à 50 % en poids de In, en plus par rapport au premier mode de réalisation. Un troisième mode de réalisation contient, en plus du premier mode de réalisation, de 0,1 à 5 % en poids de Cu et de 0,1 à 5 % en poids d'un ou de plusieurs éléments sélectionnés parmi In, Bi, Ni, Au, Sb, Zn, Mg, La et Ce. Dans la structure représentée dans la figure 1 (a) selon l'invention, on observe que de fins cristaux β-Sn primaires sont formés et les espaces entre eux sont remplis d'une fine structure cristalline eutectique, tandis que dans la structure de la figure 1 (b) ou (c) d'un exemple comparatif ne contenant pas d'aluminium, des cristaux β-Sn primaires bruts constituent la majeure partie du champ visuel. Le matériau de soudage sans plomb permet la formation de fins cristaux β-Sn primaires, permettant ainsi la formation d'une fine structure coagulée indépendante de la vitesse de refroidissement au cours de la mise en oeuvre, et une réduction de la quantité de Ag utilisé.
PCT/JP2003/000470 2002-01-22 2003-01-21 Materiau de soudage sans plomb WO2003061897A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002012446A JP2003211283A (ja) 2002-01-22 2002-01-22 鉛フリーはんだ材料
JP2002-12446 2002-01-22

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005090622A1 (fr) * 2004-03-24 2005-09-29 Agency For Science, Technology And Research Alliage de soudure exempt de plomb
EP1647352A1 (fr) * 2004-10-16 2006-04-19 Stannol GmbH Matériau de brasure
CN101549441B (zh) * 2008-04-01 2011-06-29 东莞市中实焊锡有限公司 一种无铅焊料
CN114850725A (zh) * 2022-05-24 2022-08-05 雅拓莱焊接科技（惠州）有限公司 超薄锡铋系预成型焊环及其制备工艺

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DE10319888A1 (de) 2003-04-25 2004-11-25 Siemens Ag Lotmaterial auf SnAgCu-Basis
JP4669877B2 (ja) * 2005-07-14 2011-04-13 有限会社ソフィアプロダクト 酸化物接合用はんだ合金
US7749340B2 (en) * 2005-10-24 2010-07-06 Indium Corporation Of America Technique for increasing the compliance of lead-free solders containing silver
CN100351035C (zh) * 2005-10-28 2007-11-28 亚通电子有限公司 无铅焊料
CN100364713C (zh) * 2005-12-12 2008-01-30 黄德欢 一种Ag-Al-Cu-Ni-Sn系无铅焊锡
CN100366376C (zh) * 2005-12-23 2008-02-06 南京航空航天大学 含铈的Sn-Cu-Ni钎料
JP5376553B2 (ja) * 2006-06-26 2013-12-25 日立金属株式会社 配線用導体及び端末接続部
JP4811661B2 (ja) * 2006-11-30 2011-11-09 三菱マテリアル株式会社 ボイド発生の少ないＡｕ−Ｓｎ合金はんだペースト
JP2008142729A (ja) * 2006-12-07 2008-06-26 Hitachi Metals Ltd アルミニウム部材直接接続用はんだ
JP4811663B2 (ja) * 2006-12-28 2011-11-09 三菱マテリアル株式会社 ボイド発生の少ないＳｎ−Ａｕ合金はんだペースト
JP5019179B2 (ja) 2007-03-29 2012-09-05 日立金属株式会社 はんだ合金およびそれを用いたガラス接合体
KR20110044793A (ko) * 2008-08-21 2011-04-29 에이저 시스템즈 인크 Ｓｎ-필름 내의 휘스커의 완화
CN102059469B (zh) * 2010-11-29 2012-10-10 力创(台山)电子科技有限公司 一种用于铜铝复合管的环保焊环的制备方法
WO2012137901A1 (fr) * 2011-04-08 2012-10-11 株式会社日本スペリア社 Alliage de brasure
JP5765109B2 (ja) * 2011-07-21 2015-08-19 住友金属鉱山株式会社 サーバー用ＣＰＵ向け無鉛Ｉｎ基はんだ合金及びその製造方法
CN103056543B (zh) * 2013-01-18 2015-03-25 江苏师范大学 一种含Yb、Al、B的纳米无铅钎料
CN105103279B (zh) * 2013-05-10 2018-03-23 富士电机株式会社 半导体装置及半导体装置的制造方法
CN103381526B (zh) * 2013-06-22 2016-02-03 宁波市鄞州品达电器焊料有限公司 一种新型焊料

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JP2000141078A (ja) * 1998-09-08 2000-05-23 Nippon Sheet Glass Co Ltd 無鉛ハンダ
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005090622A1 (fr) * 2004-03-24 2005-09-29 Agency For Science, Technology And Research Alliage de soudure exempt de plomb
EP1647352A1 (fr) * 2004-10-16 2006-04-19 Stannol GmbH Matériau de brasure
CN101549441B (zh) * 2008-04-01 2011-06-29 东莞市中实焊锡有限公司 一种无铅焊料
CN114850725A (zh) * 2022-05-24 2022-08-05 雅拓莱焊接科技（惠州）有限公司 超薄锡铋系预成型焊环及其制备工艺
CN114850725B (zh) * 2022-05-24 2024-04-26 雅拓莱焊接科技（惠州）有限公司 超薄锡铋系预成型焊环及其制备工艺

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TW200302147A (en) 2003-08-01

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