WO2009143677A1 - 高熔点无铅焊料及其生产工艺 - Google Patents
高熔点无铅焊料及其生产工艺 Download PDFInfo
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- WO2009143677A1 WO2009143677A1 PCT/CN2008/071738 CN2008071738W WO2009143677A1 WO 2009143677 A1 WO2009143677 A1 WO 2009143677A1 CN 2008071738 W CN2008071738 W CN 2008071738W WO 2009143677 A1 WO2009143677 A1 WO 2009143677A1
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- melting point
- free
- high melting
- solder
- alloy
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C12/00—Alloys based on antimony or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- 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 lead-free solder, and more particularly to a high melting point lead-free solder for chip soldering and IC package bonding. Background technique
- Chip soldering and IC package soldering require solder to have a melting point higher than 260 ° C. Low solder melting points can cause subsequent solder joints to break pre-welded solder joints, thus affecting solder quality.
- the high melting point solder used for chip soldering and IC package soldering is a lead high melting point solder. Since this solder contains lead elements harmful to the human body, it will be banned in the next few years, so everyone is looking for Replaces lead-free solder with lead high melting point solder.
- solders with melting points above 260 There are two kinds of lead-free solders with melting points above 260 , one is the well-known expensive Au80 (wt%)-Sn20 (wt) solder, because the mass percentage of this solder gold is about 80%, which leads to its The price is very expensive and the scope of application is greatly limited.
- the other one is the high melting point lead-free bait material disclosed in Patent 01823276.0, the alloy composition of which is 2:1 ⁇ 18 ⁇ % of eight 8 and 98 ⁇ 1:% ⁇ 82 ⁇ 1:%, compared with the previous one
- the solder disclosed in this patent has been significantly reduced in price; however, since silver is also a precious metal, and its content in solder is up to 18 wt%, the lowest is 2wt%, considering the cost, this high melting point lead-free solder is not an ideal material, so the industry urgently needs a low precious metal content, not even
- the technical problem to be solved by the present invention is to provide a low-cost, high-melting lead-free solder which can be used for die bonding and IC package soldering.
- the high melting point lead-free solder of the present invention comprises the following alloy, which is composed of 2:% to 5 ⁇ % of Sb and 98% to 95"1%, and the solid phase line of the alloy is not Below 270 ° C, the liquidus is not higher than 310 ° C. Since the Bi-Sb alloy is an infinitely miscible alloy, the solid and liquid point of the alloy increases with the increase of the Sb content, from the alloy phase diagram shown in Figure 1. It can be seen that the lowest solid phase point is 270; after the Sb content is increased to 5 ⁇ %, the liquidus point is lower than 310 ° C.
- the lead-free solder of the present invention is inexpensive, and has a low-cost, conventional lead-containing solder. Compared to, it is more environmentally friendly.
- the solder further contains 0.5 wt% to 1.5 wt% of silver.
- the purpose of adding silver is to increase the solder diffusion rate to improve the solderability of the solder, and the added silver mass percentage is low, which does not significantly increase the solder cost.
- the solder further contains 0.003 wt% to 0.01% of phosphorus.
- the phosphorus element can coat the liquid surface of the Bi-Sb-Ag solder with a thin protective film of phosphorus oxyacid salt, which prevents the formation of welding slag and improves the welding quality.
- Another problem to be solved by the present invention is to provide a production process for producing the above high melting point lead-free solder.
- the production process of the present invention comprises the following steps: A. A certain amount of Bi and Sb are respectively taken according to the composition ratio requirement ; B. The Bi is melted by using stainless steel crucible or graphite crucible and then heated to 500 ⁇ 60 (TC ; C ; Add Sb to stainless steel crucible or graphite crucible, stir well and let stand for a period of time to make the ingredients fully uniform; D, cool the alloy to normal temperature.
- the high melting point lead-free solder produced by this production process does not contain precious metals. The cost of the solder is significantly reduced, and the manufacturing process is simple.
- solder may be formed into a soldering piece or a soldering ring or a solder paste, and different shapes or forms of the dip material may be used according to different use requirements, which is convenient to use.
- the manufacturing process of the soldering piece or the welding ring is as follows: a. bonding the alloy into a paste by using a bonding agent; b, coating the paste in the middle of the double silver foil; c. The silver flakes containing the paste are preformed into solder pieces of the desired shape. Pasting the solder between the silver sheets prevents the solder from leaking, and the adhesive also acts as a soldering aid to improve the solderability of the workpiece.
- Figure 1 is a phase diagram of a Bi-Sb binary alloy. detailed description
- the high melting point lead-free solder of the present invention comprises a Bi-based alloy having a Bi content of 95 wt% to 98 wt%, which is alloyed after adding Sb, wherein the content of Sb is 2 wt% to 5 wt%.
- the prepared solder has a solid phase point of not less than 27 (TC, the liquidus point is not less than 310 ° C. It can replace lead-containing solder for chip soldering and IC package soldering.
- the percentage of weld diffusivity described in Table 1 is compared to the solder commonly used in the prior art, and the solder alloy composition is Pb-10Sn.
- the table below shows that adding an appropriate amount of Ag can significantly increase the diffusion rate of the alloy.
- the amount of Ag added should not be too much, about lwt% or slightly lower, and satisfactory results can be obtained.
- the above-mentioned silver is not directly added to the alloy, but only when the high melting point lead-free tantalum product is produced.
- the method of adding silver when manufacturing a soldering piece is hereinafter.
- Another problem to be solved by the present invention is to provide specific smelting processes and products in combination with alloy characteristics.
- the smelting process of the alloy in the high melting point lead-free solder of the present invention selecting the alloy combination of the best performance, and performing the actual amount calculation.
- the Bi is first melted and then heated to 500 to 60 (TC, then added to Sb, and stirred thoroughly, and allowed to stand for a while, so that the components are sufficiently uniform and completely alloyed, and then cooled to room temperature.
- the whole process can be covered with charcoal surface, and the use of charcoal to cover the alloy solution can prevent the alloy solution from being oxidized during the smelting process.
- solder When the solder is used, it adopts two kinds of products: 1 composite strip or composite sheet, and then pre-formed as needed, such as an annulus, a soldering piece; 2 solder paste.
- the method of manufacturing the composite strip (sheet): 1 is made into a paste by Bi-Sb alloy, wherein the Bi-Sb powder is made into a paste of suitable viscosity by a special adhesive, and the ratio is based on the proportion of the alloy component.
- the paste is applied between the two very thin layers of Ag, with a special adhesive (also used as a co-agent). Bonded into a composite tape of a certain strength, and punched into various preformed soldering pieces as needed. When used, the preformed sheet is placed at each desired position, and enters the hot zone. The temperature is between 340 ° C and 360 ° C.
- the multilayer composite sheet will be alloyed with Ag ⁇ immediately after the solder is melted, and the formation is completed. The required solder joints for the required components.
- Solder paste manufacturing method Firstly, the high melting point lead-free solder is made into a solder powder with a particle size of 5 or more; the solder powder and the flux are uniformly mixed to form a paste, and finally the prepared solder paste is softened. In a bag or other packaging container.
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- Engineering & Computer Science (AREA)
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Description
高熔点无铅焊料及其生产工艺 技术领域
本发明涉及一种无铅焊料， 特别是指芯片焊接以及 IC封装悍接 用高熔点无铅焊料。 背景技术
芯片焊接以及 IC封装焊接要求焊料的熔点高于 260°C， 焊料熔 点低会导致后期悍接破坏先期焊接好的焊点， 从而影响焊接质量。通 常芯片焊接以及 IC封装焊所用的高熔点焊料为有铅高熔点焊料， 由 于这种焊料中含有对人体有害的铅元素，其在未来几年内将会被禁止 使用， 所以目前大家都在寻找能够替代有铅高熔点焊料的无铅焊料。
现有的熔点在 260Ό以上的无铅焊料有两种， 一种是众所周知的 价格昂贵的 Au80 (wt%) -Sn20 (wt ) 焊料， 由于这种焊料金的 质量百分比在 80%左右， 导致其价格很贵， 应用范围受到很大的限 制。
另一种为专利 01823276.0中所揭示的高熔点无铅悍料， 其合金 成分为 2 1:%〜18^%的八8和98¥1:%〜82¥1:%的 ， 相比前一种高 元铅焊料来说，该专利中所揭示的焊料从价格上已经明显地降低 了； 但是， 由于银同样是贵金属， 而且其在焊料中的含量最高是可能 达到 18wt%, 最低时也为 2wt%， 从成本方面来考虑， 这种高熔点无 铅焊料并不是理想的材料，所以业界急需一种贵金属含量低，甚至不
替换页（细则第 26条)
含贵金属的高熔点无铅焊料。 发明内容
本发明要解决的技术问题是提供一种价格低廉的高熔点无铅悍 料， 这种高熔点无铅焊料可以用于芯片焊接以及 IC封装焊接。
为解决上述技术问题， 本发明高熔点无铅焊料包含下述合金， 该 合金由 2 1:%〜5^%的 Sb和 98^%〜95 "1%的 组成，该合金的 固相线不低于 270°C， 液相线不高于 310°C。 由于 Bi— Sb合金系属 于无限互溶合金， 合金固、 液相点随 Sb含量的提高而提高， 从图 1 所示的合金相图中可以看出， 其最低固相点为 270 ; Sb含量提高 到 5^%后其液相点低于 310°C。 本发明无铅焊料由于不含贵金属， 价格低廉， 与传统的含铅焊料相比， 更加环保。
作为本发明高熔点无铅焊料的改进， 该焊料还含有 0.5wt%〜 1.5wt%的银。添加银元素的目的是提高焊接扩散率， 以改善焊料的 可焊性能， 而且加入的银质量百分比很低， 不会显著增加焊料的成 本。
作为本发明高熔点无铅焊料的进一步改进， 该焊料还含有 0.003wt%〜0.01 ％的磷。 磷元素能够使 Bi- Sb- Ag焊料的液态表 面上覆盖一层很薄的磷含氧酸盐保护膜，起到防止焊渣形成的作用， 可以提高焊接质量。
本发明要解决的另一个问题是提供一种生产上述高熔点无铅焊 料的生产工艺。
替换页（细则第 26条)
为了解决上述技术问题， 本发明生产工艺包括如下步骤： A、 按 照成分比例要求分别取一定量的 Bi和 Sb; B、 使用不锈钢坩埚或石 墨坩埚将 Bi熔化后升温至 500〜60(TC ; C, 向不锈钢坩埚或石墨坩 埚加入 Sb, 并充分搅拌后静置一段时间， 使其中成分充分均匀； D， 将合金冷却至常温。 采用这种生产工艺制得的高熔点无铅焊料不含 贵金属， 显著地降低了焊料的成本， 而且其制作工艺过程简单。
进一步地， 可将所述焊料制成焊片或焊环或焊膏，根据不同使用 要求， 采用不同形状或形态的悍料， 方便使用。
上述焊片或焊环的制作过程如下： a、 采用起助焊作用的粘结剂 将所述合金粘结成膏状体； b、 将膏状体涂覆在双层银薄片中间； c、 将含有膏状体的银薄片预成型为所需形状的焊片。将焊料制成膏状涂 覆在银片之间可以防止焊料撒漏，而且粘结剂还起助焊作用，可以提 高工件的可焊 ¾i。 附图说明
图 1为 Bi— Sb二元合金相图。 具体实施方式
本发明高熔点无铅焊料包含以 Bi为基合金，合金中 Bi的含量为 95wt %〜98wt%， 再添加 Sb以后经过合金化制成的，其中 Sb的含量 为 2wt%〜5wt %。制成的焊料的固相点不低于 27(TC，液相点不髙于 310°C。 可以取代含铅焊料进行芯片焊接以及 IC封装焊接。
替换页（细则第 26条)
由于 Bi— Sb合金系属于无限互溶合金， 合金固、液相点随 Sb含 量的提高而提高， 经过实验得出如图 1所示的二元合金相图， 当 Sb 的含量等于 2^%时，其最低固相点高于 27CTC，当 Sb的含量等于 5wt% 时， 其最低液相点低于 310°C， 由此我们可以得出焊料的固相点温度 不低于 27CTC， 其液相点不高于 310°C。
下表列出了 Bi— Sb合金中， 随 Sb含量的变化，对焊料扩散率及 合金液相点的影响。
表 1
下表列出了加入适量 Ag， 可明显提高合金的扩散率。 为了降低 成本， Ag的加入量不宜太多， 约 lwt%或稍低些， 即可得到满意的效 果。
替换页（细则第 26条)
表 2
表 2和表 3所述的悍接扩散率百分比是与现有技术中常用的悍料 作比较， 该焊料合金成分为 Pb- 10Sn。
由表 1和表 2对比可知， 加入 lwt%的银能够明显提高焊料的扩 散率，改善其可焊性； 由表 2和表 3对比可知，随着银加入量的提高， 焊料的扩散率也不断地得到提高，但是为了控制焊料的成本， 银的加 入量为 lwt%时， 可取得较佳的性价比。
当然， 上述银并不是直接加入到合金中去的， 只是在制作高熔点 无铅悍料产品时才加入银。 例如下文中制作焊片时添加银的方式。
同时， 为了提髙焊料的焊接质量， 防止焊点中夹杂焊渣， 可在加 入银的同时加入 0. 003wt %〜0. 01wt %的磷由于。 磷元素能够使
替换页（细则第 26条)
Bi-Sb-Ag 焊料的液态表面上覆盖一层很薄的磷含氧酸盐保护膜， 这 种保护膜能够防止焊渣的形成， 可以提高焊接质量。
本发明要解决的另一个问题是结合合金特性， 提供具体的熔炼 工艺以及产品。
本发明高熔点无铅焊料中合金的熔炼工艺： 选择最佳性能的合 金组合， 进行实际量配料计算。 使用不锈钢坩埚 （或石墨坩埚）， 先 将 Bi熔化后升温至 500〜60(TC， 然后加入 Sb，并充分搅拌后静置一 段时间， 让其中成分充分均匀并完全合金化后再冷却至常温。整个过 程采用木炭表面覆盖即可，使用木炭覆盖合金溶液可以防止合金溶液 在熔炼过程中被氧化。 ·
焊料使用时， 采用两种形态的产品： ①复合带状或复合片状， 再根据需要冲制预成型片， 如悍环， 焊片； ②焊膏。
复合带状 （片状） 的制作方法： ①以 Bi-Sb合金制作成膏状体， 其中由特殊粘接剂将 Bi- Sb 粉制成合适粘度的膏体， 按合金成分比 例，将此种膏体涂敷在双层极薄的 Ag薄片中间，靠特殊的粘接剂（也 起助悍剂用）。 粘接成具有一定强度的复合带， 根据需要冲制成各种 预成型焊片。使用时将预成型片放置在各需要位置， 进入热区， 温度 在 340°C〜360°C间， 多层复合片会在其中的焊料先熔化后立刻与 Ag ^ 进行合金化反应， 达到形成所需的成分要求的焊点。
焊膏的制作方法： 首先将高熔点无铅焊料制成颗粒度达到 5 级 以上的焊粉； 将焊粉与助焊剂混合均匀后制成悍膏 ·, 最后将制成的焊 膏装进软袋或其他包装容器中。
替换页（细则第 26条)
Claims
1. 一种高熔点无铅悍料， 其特征在于： 其包括下述合金， 该合 金由 2«^ %〜5«^ %的 Sb和 98«^ %〜95«^ %的 Bi组成， 该合金的固 相点不低于 270°C， 液相点不高于 310°C。
2. 如权利要求 1所述的高熔点无铅悍料， 其特征在于： 所述悍 料还含有 0. lwt %〜1. 5wt %的银。
3. 如权利要求 2所述的高熔点无铅悍料， 其特征在于： 所述悍 料还含有 0. 003wt %〜0. 01«^ %的磷。
4. 一种权利要求 1所述的高熔点无铅悍料的生产工艺， 其特征 在于： 包括如下歩骤：
A、 按照成分比例要求分别取一定量的 Bi和 Sb;
B、 使用不锈钢坩埚或石墨坩埚将 Bi熔化后升温至 500〜600°C ;
C、 向不锈钢坩埚或石墨坩埚加入 Sb， 并充分搅拌后静置一段时 间， 使其中成分均匀；
D、 将合金冷却至常温。
5. 如权利要求 4所述的高熔点无铅悍料的生产工艺， 其特征在 于： 整个过程采用木炭覆盖在合金溶液表面。
6. 如权利要求 4所述的高熔点无铅悍料的生产工艺， 其特征在 于： 所述悍料被制成悍片或悍环或悍膏。
7. 如权利要求 6所述的高熔点无铅悍料的生产工艺， 其特征在 于： 所述悍片或悍环的制作过程包括：
a、 采用起助悍作用的粘结剂将所述合金粘结成膏状体；
b、 将膏状体涂覆在双层银薄片中间；
c、 将含有膏状体的银薄片预成型为所需形状的焊片或悍环。
8. 如权利要求 6所述的高熔点无铅悍料的生产工艺， 其特征在 于： 所述高熔点无铅悍料首先被制成悍粉； 悍粉在与助悍剂混合均匀 后制成悍膏。
9. 如权利要求 8所述的高熔点无铅悍料的生产工艺， 其特征在 于： 所述悍粉的颗粒度达到 5级以上。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100283683A CN101332544A (zh) | 2008-05-28 | 2008-05-28 | 高熔点无铅焊料及其生产工艺 |
| CN200810028368.3 | 2008-05-28 |
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| WO2009143677A1 true WO2009143677A1 (zh) | 2009-12-03 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014115699A1 (ja) * | 2013-01-28 | 2014-07-31 | ニホンハンダ株式会社 | ダイボンド接合用はんだ合金 |
| WO2020079151A1 (fr) * | 2018-10-19 | 2020-04-23 | Dehon Sa | Alliage composite pour brasure et utilisation d'un tel alliage |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101332544A (zh) * | 2008-05-28 | 2008-12-31 | 广州瀚源电子科技有限公司 | 高熔点无铅焊料及其生产工艺 |
| KR101738841B1 (ko) * | 2010-06-30 | 2017-05-22 | 센주긴조쿠고교 가부시키가이샤 | Ｂｉ-Ｓｎ계 고온 땜납 합금으로 이루어진 고온 땜납 이음 |
| 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 |
| CN106392366B (zh) * | 2016-12-02 | 2019-07-19 | 北京康普锡威科技有限公司 | 一种BiSbAg系高温无铅焊料及其制备方法 |
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| JP2007301570A (ja) * | 2006-05-08 | 2007-11-22 | Honda Motor Co Ltd | はんだ合金 |
| CN101332544A (zh) * | 2008-05-28 | 2008-12-31 | 广州瀚源电子科技有限公司 | 高熔点无铅焊料及其生产工艺 |
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2008
- 2008-05-28 CN CNA2008100283683A patent/CN101332544A/zh active Pending
- 2008-07-24 WO PCT/CN2008/071738 patent/WO2009143677A1/zh active Application Filing
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| JPH11320177A (ja) * | 1998-05-13 | 1999-11-24 | Murata Mfg Co Ltd | はんだ組成物 |
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| CN1507499A (zh) * | 2001-05-28 | 2004-06-23 | ����Τ�����ʹ�˾ | 高温无铅焊料用组合物、生产方法及元件 |
| JP2004114093A (ja) * | 2002-09-26 | 2004-04-15 | Sumitomo Metal Mining Co Ltd | 高温ろう材 |
| JP2007301570A (ja) * | 2006-05-08 | 2007-11-22 | Honda Motor Co Ltd | はんだ合金 |
| CN101332544A (zh) * | 2008-05-28 | 2008-12-31 | 广州瀚源电子科技有限公司 | 高熔点无铅焊料及其生产工艺 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014115699A1 (ja) * | 2013-01-28 | 2014-07-31 | ニホンハンダ株式会社 | ダイボンド接合用はんだ合金 |
| KR20150046337A (ko) * | 2013-01-28 | 2015-04-29 | 니혼한다가부시끼가이샤 | 다이 본드 접합용 땜납 합금 |
| JP6038187B2 (ja) * | 2013-01-28 | 2016-12-07 | ニホンハンダ株式会社 | ダイボンド接合用はんだ合金 |
| KR101711411B1 (ko) | 2013-01-28 | 2017-03-02 | 니혼한다가부시끼가이샤 | 다이 본드 접합용 땜납 합금 |
| US10189119B2 (en) | 2013-01-28 | 2019-01-29 | Nihon Handa Co., Ltd. | Solder alloy for die bonding |
| WO2020079151A1 (fr) * | 2018-10-19 | 2020-04-23 | Dehon Sa | Alliage composite pour brasure et utilisation d'un tel alliage |
| FR3087369A1 (fr) * | 2018-10-19 | 2020-04-24 | Dehon Sa | Alliage de brasure et utilisation d'un tel alliage |
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| Publication number | Publication date |
|---|---|
| CN101332544A (zh) | 2008-12-31 |
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