CN1977368A - 软钎焊方法、芯片焊接用软钎料颗粒、芯片焊接软钎料颗粒的制造方法及电子零件 - Google Patents

软钎焊方法、芯片焊接用软钎料颗粒、芯片焊接软钎料颗粒的制造方法及电子零件 Download PDF

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CN1977368A
CN1977368A CNA2005800215356A CN200580021535A CN1977368A CN 1977368 A CN1977368 A CN 1977368A CN A2005800215356 A CNA2005800215356 A CN A2005800215356A CN 200580021535 A CN200580021535 A CN 200580021535A CN 1977368 A CN1977368 A CN 1977368A
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soft solder
alloy
chips welding
particle
solder
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上岛稔
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Senju Metal Industry Co Ltd
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    • 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
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    • 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
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    • 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
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    • 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
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Abstract

为了得到在芯片焊接接合电子零件的半导体元件和基板时，尽管是无铅软钎料的颗粒，但产生的空隙仍然少的颗粒，在软钎焊过热时，在Sn为主成分的无铅软钎料合金的表面形成：无色透明的由30～50原子％的O、5～15原子％的P以及余量实质Sn构成的保护膜；以及由10～30原子％的In、40～60原子％的O、5～15原子％的P以及余量实质Sn构成的保护膜，从而得到该颗粒，其厚度为0.05～1mm，形状与基板大致相同。

Description

软钎焊方法、芯片焊接用软钎料颗粒、芯片焊接软钎料颗粒的制造方法及电子零件
技术领域
本发明涉及接合电子零件的半导体元件和基板的芯片焊接(diebonding)用的软钎料颗粒(Solder Pellet)、以及用软钎料接合半导体元件和基板的电子零件。
背景技术
BGA、CSP等高性能电子零件，其半导体元件和基板是由接合材料芯片焊接接合起来的。所谓的芯片焊接，是指将切割硅晶片而得到的半导体元件固定在电子零件的基板上的工序。对于芯片焊接半导体元件和基板而言，在使用电子设备时有时从半导体元件发热而半导体本身因热影响出现性能恶化或热损伤，因此，接合半导体元件和基板，将从半导体元件放出的热量从基板释放。另外，芯片焊接接合还用于从半导体元件接地。作为该芯片焊接用接合用一般使用的材料是粘接性树脂或软钎料。如果只是以从半导体元件放热为目的，则粘接性树脂亦可，但在以放热和接地为目的的情况下，使用导热性良好、而且导电性良好的软钎料。
在以放热为目的的芯片焊接接合中，理想的是半导体元件和基板完全接合，在接合面不可存在空隙(void)。例如在用粘接性树脂进行接合时，若在粘接性树脂中存在很小的气泡，则该气泡被压溃而成为大的空隙。因此，对于粘接性树脂而言，为了消除粘接性树脂中的气泡，进行在真空中搅拌粘接性树脂、从而消除内部的气泡的脱泡处理。另一方面，对于在使用了软钎料的接合中产生空隙的情况，在软钎焊时使用的助熔剂气化，若其残留在软钎焊部则成为空隙，另外，若软钎料的润湿性差，则在软钎焊时出线熔融的软钎料的未润湿的部分，其成为空隙。
一般而言，软钎焊使用助熔剂，但若使用助熔剂，则会残留助熔剂残渣，该助熔剂残渣吸湿而成为产生腐蚀生成物或降低绝缘电阻的原因，因此，在要求高可靠性的电子设备中进行的是不使用助熔剂的软钎焊、即无助熔剂软钎焊。无助熔剂的软钎焊是指，将软钎料置于软钎焊部，然后在氢和氮的混合气体气氛中对其进行加热。若在无助熔剂的状态下进行软钎焊，则不存在因助熔剂的气化而产生空隙的问题，但软钎料的润湿性受到较大影响。即，在软钎焊中助熔剂还原除去软钎焊部的氧化物，并且降低熔融的软钎料的表面张力，因此，软钎料良好地润湿扩展。但是，在芯片焊接接合时，若进行无助熔剂接合，则混合气体气氛无法得到如助熔剂那样强的活性。因此，在进行芯片焊接接合时，在此所用的软钎料必须是软钎料本身具有优异的润湿性。
本申请人，对于芯片焊接用颗粒等成形焊料(form solder)，公开有一种在常温下将固体的物质均匀地涂敷在表面的成形焊料，以避免成形焊料彼此粘着(专利文献1)。
专利文献1：特开平9-29478
一直以来，用于芯片焊接接合用的软钎料是Sn-Pb系软钎料。但是，Sn-Pb系软钎料由于铅公害的问题而限制其使用，到今天变成使用不含铅的所谓“无铅软钎料”。该无铅软钎料是在Sn或以Sn为主成分中适当添加Ag、Cu、Sb、Bi、In、Ni、Cr、Mo、Ge、Ga、P等第三元素而成。在Sn-Pb系软钎料中，由于润湿性好，所以即使在无助熔剂的状态下进行芯片焊接接合，产生的空隙也较少。但是，无铅软钎料与Sn-Pb系软钎料相比由于润湿性差，所以在无助熔剂的芯片焊接接合中产生较多空隙。若在这样进行芯片焊接接合时，产生大量的空隙，则不仅散热变差，而且接合强度也变弱，因产品使用时的电发热而使得基板整体反复膨胀收缩，因反复热疲劳而在接合部产生裂纹，阻碍从半导体元件的散热，使器件的性能下降。
发明内容
本发明提供一种尽管使用润湿性差的无铅软钎料，但在芯片焊接接合中极少产生空隙的芯片焊接接合用软钎料颗粒以及空隙少的电子零件。
本发明人已查明：通过在Sn为主成分的无铅软钎料的表面，形成由Sn、O和P构成的无色透明的保护皮膜或由Sn、In、O和P构成的无色透明的保护皮膜，从而在软钎料过热时，防止在软钎料表面形成牢固的看上去为黄色到褐色的SnO2或In2O3的氧化皮膜，进而，因过热而保护膜容易粉碎，熔融软钎料本来的流动性、反应性提高，从而完成了本发明。
本发明是一种芯片焊接用软钎料颗粒，接合电子零件的半导体元件和基板，其中，该颗粒是如下一种颗粒，即，在软钎焊过热时，在Sn为主成分的无铅软钎料合金的表面形成：无色透明的由30～50原子.％的O、5～15原子％的P以及余量实质Sn构成的保护膜；以及由10～30原子％的In、40～60原子.％的O、5～15原子％的P以及余量实质Sn构成的保护膜，保护膜的厚度优选为0.5～20nm，更优选为1～5nm。进而，提供一种芯片焊接用软钎料颗粒的软钎焊方法，该芯片焊接用软钎料颗粒接合电子零件的半导体元件和基板，其中，通过软钎焊时的加热，在Sn为主成分的无铅软钎料合金的表面形成：无色透明的厚度为0.5～20nm，且由30～50原子.％的O、5～15原子％的P以及余量实质Sn构成的保护膜。
另外，另一发明是一种电子零件，其中，在接合电子零件的半导体元件和基板的芯片焊接用软钎料颗粒中，利用如下所述的颗粒对半导体元件和基板进行芯片焊接接合，而且该接合面的空隙率在10％以下，所述颗粒是在软钎焊过热时，在Sn为主成分的无铅软钎料合金的表面形成有：无色透明的由30～50原子.％的O、5～15原子％的P以及余量实质Sn构成的保护膜；以及由10～30原子％的In、40～60原子.％的O、5～15原子％的P以及余量实质Sn构成的保护膜。
(发明效果)
本发明的芯片焊接接合用软钎料颗粒，由于使用无铅软钎料，所以即使电子设备出现故障而被废弃处理于室外或地下，也不会因酸雨而溶解出铅，因此，不会引起环境污染。另外，本发明的软钎料颗粒，尽管使用本来润湿性差的无铅软钎料，但由于现在润湿性好，所以很少产生空隙。而且，本发明的电子零件，由于半导体元件和基板之间空隙少，所以可得到充分的接合强度，可靠性良好。
具体实施方式
本发明所使用的无铅软钎料是Sn100％以及Sn为主成分的合金。Sn的单体也有作为无铅软钎料使用的情况，或者也有在Sn中添加第三元素来使用的情况。适合本发明使用的无铅软钎料是Sn系合金、Sn-Cu系合金、Sn-Ag系合金、Sn-Ag-Cu系合金、Sn-Bi系合金、Sn-In系合金的任一种。在此所称的“系”是指在主要成分中适当添加了所述第三元素的物质。例如，所谓的Sn-Ag系是除了Sn-Ag以外，在该合金中适当添加了第三元素的物质。
为了在本发明的芯片焊接接合用软钎料颗粒使用的无铅软钎料上形成：无色透明的由30～50原子.％的O、5～15原子％的P以及余量实质Sn构成的保护膜；以及由10～30原子％的In、40～60原子.％的O、5～15原子％的P以及余量实质Sn构成的保护膜，预先需要在软钎料合金中添加0.0001～0.02质量％的P。如果P的添加量少于0.0001质量％，则难以形成这些保护膜，难以抑制黄色的SnO2膜的形成，然而若添加得多于0.02质量％，则软钎料本身的液相线温度上升、润湿性下降，并且在软钎料组织内部较大地结晶出Sn-P的化合物，机械性能下降。
本发明的芯片焊接用软钎料颗粒，如果厚度比0.05mm薄，则在作为接合部的半导体元件和基板之间存在的软钎料的量过少，不仅接合强度不够，而且容易产生空隙。然而，如果颗粒的厚度超过1mm，则软钎料的量过多，接合后剩余的软钎料从半导体元件较多地露出，软钎料附着于不需要的部位，或者在之后的引线焊接时与引线接触。
另外，本发明的芯片焊接用软钎料颗粒，形状和接合的半导体元件大致相同。如果软钎料颗粒相比于半导体元件过小，则软钎料不能遍及半导体元件整个区域，进而，由于空隙也增加使得接合强度变弱。然而，如果软钎料颗粒相比于半导体元件过大，则由于在从元件露出的软钎料颗粒上面约束力消失，随着表面张力变成球状，元件下部的软钎料量下降，结果不仅会由于热疲劳引起接合可靠性下降，而且从元件露出的软钎料附着于不适当的部位而成为引起短路事故的原因。
本发明的电子零件，是用添加了1～200ppm的P的合金芯片焊接接合半导体元件和基板的零件，接合面的空隙所占的面积比例(空隙率)在10％以下。一般地说，若半导体元件和基板的接合面的空隙率大，则为了增加导热性和接合强度，需要进行增加软钎料的厚度、降低基板的热膨胀等较大地改变设计，而成为逆向实施现代的细距(fine pitch)安装的情况。接合强度也变弱，因产品使用时的电发热使得基板整体反复膨胀收缩，因反复热疲劳而在接合部产生裂纹，阻碍从半导体元件散热，使器件的性能下降。因此，在本发明中，使空隙率在10％以下。
实施例1
通过软钎料颗粒将10×10×0.3(mm)的半导体元件芯片焊接接合在30×30×0.3(mm)的基板(镀镍的铜基板)上。使用的无铅软钎料如表1所示，是在Sn-Cu-Ni系软钎料中添加了P的软钎料。将软钎料颗粒的形状成形为10×10×0.1(mm)，将该软钎料颗粒夹在半导体元件和基板之间，在氧浓度为50ppm的氢氮混合气体气氛中，在235℃以上加热3分钟，峰值温度为280℃，以总回流(reflow)时间为15分钟进行了回流。通过xps测定了在表面产生的保护膜的厚度和金属组成。进而，通过透过X射线装置观察了该芯片焊接接合的部分的空隙，测量了空隙率。
实施例2
通过软钎料颗粒将10×10×0.3(mm)的半导体元件芯片焊接接合在30×30×0.3(mm)的基板(镀镍的铜基板)上。使用的无铅软钎料如表1所示，是在Sn-Ag-Cu系软钎料中添加了P的软钎料。将软钎料颗粒的形状成形为10×10×0.1(mm)，将该软钎料颗粒夹在半导体元件和基板之间，在氧浓度为50ppm的氢氮混合气体气氛中，在235℃以上加热3分钟，峰值温度为280℃，以总回流时间为15分钟进行了回流。通过XPS测定了在表面产生的保护膜的厚度和金属组成。进而，通过透过X射线装置观察了该芯片焊接接合的部分的空隙，测量了空隙率。
实施例3
通过软钎料颗粒将10×10×0.3(mm)的半导体元件芯片焊接接合在30×30×0.3(mm)的基板(镀镍的铜基板)上。使用的无铅软钎料如表1所示，是在Sn-In系软钎料中添加了P的软钎料。将软钎料颗粒的形状成形为10×10×0.1(mm)，将该软钎料颗粒夹在半导体元件和基板之间，在氧浓度为50ppm的氢氮混合气体气氛中，在235℃以上加热3分钟，峰值温度为280℃，以总回流时间为15分钟进行了回流。通过xps测定了在表面产生的保护膜的厚度和金属组成。进而，通过透过X射线装置观察了该芯片焊接接合的部分的空隙，测量了空隙率。
实施例1～3的软钎料颗粒组成、在表面产生的保护膜的厚度和金属组成以及空隙率的测量结果如表1～3所示。
在此，保护膜的厚度及金属组成通过xps，以0.2nm单位进行溅射，收集深度方向的信息，另外，空隙率是使用X射线透过型的截面观察装置以50倍进行了测定。
[表1]
  组成(Wt％)   保护膜组成(At％)   保护膜厚度(nm)   空隙率(％)
  Sn   Cu   Ni   P(ppm)   Sn   O   P
 实施例1   余量   0.7   0.06   10   48   44   8   1   7.0
 实施例2   余量   0.7   0.06   50   44   45   11   12   3.5
 实施例3   余量   0.7   0.06   200   51   35   14   8   4.2
 比较例1   余量   0.7   0.06   0   40   60   0   0   13.0
 比较例2   余量   0.7   0.06   400   50   36   14   18   15.0
[表2]
  组成(Wt％)   保护膜组成(At％)   保护膜厚度(μm)   空隙率(％)
  Sn   Cu   Ag   P(ppm)   Sn   O   P
 实施例1   余量   0.5   3   10   44   47   9   2   8.0
 实施例2   余量   0.5   3   50   44   49   7   12   5.8
 实施例3   余量   0.5   3   150   46   43   11   8   6.2
 比较例1   余量   0.5   3   0   33   67   0   0   17.0
 比较例2   余量   0.5   3   400   50   36   14   18   13.0
[表3]
  组成(Wt％)   保护膜组成(At％)   保护膜厚度(μm)   空隙率(％)
  Sn   In   P(ppm)   Sn   O   In   P
 实施例1   余量   15   10   12   50   25   13   2   8.0
 实施例2   余量   15   50   10   55   20   15   11   7.0
 实施例3   余量   15   150   14   56   22   8   16   6.5
 比较例1   余量   15   0   15   60   25   0   0   25.0
 比较例2   余量   15   250   15   45   24   16   15   18.0
从表1～3可以看出，利用在无铅软钎料中添加了P的软钎料进行了芯片焊接接合的电子零件，相比于与其同一组成但没有添加P的软钎料，空隙率减少了40％以上。另外，在用添加了P的软钎料进行芯片焊接接合时，空隙率在10％以下，但在用没有添加P的软钎料进行芯片焊接接合时，空隙率超过了10％。
(工业上的可利用性)
在制造本发明电子零件时，减少空隙的最佳接合方法是利用颗粒在氢氮混合气体气氛中进行芯片焊接接合，但由于氢氮混合气体较贵，所以还可以采用其他的接合方法。即，为了降低成本，在不使用氢氮混合气体而在大气中进行芯片焊接接合时，必须使用助熔剂，但本发明的芯片焊接用软钎料颗粒，即使使用助熔剂，也能够减少空隙。进而本发明的电子零件还可以利用焊膏来制造。焊膏混合了软钎料粉末和助熔剂，由于不用另外供给助熔剂，所以可进行合理的接合。

Claims (11)

1.一种芯片焊接用软钎料颗粒的软钎焊方法，该芯片焊接用软钎料颗粒接合电子零件的半导体元件和基板，该方法的特征在于，
通过软钎焊时的加热，在Sn为主成分的无铅软钎料合金的表面形成：无色透明的厚度为0.5～20nm，且由30～50原子.％的O、5～15原子％的P以及余量实质Sn构成的保护膜。
2.一种芯片焊接用软钎料颗粒，其接合电子零件的半导体元件和基板，其特征在于，
该颗粒是如下一种颗粒，即，在软钎焊加热时，在Sn为主成分的无铅软钎料合金的表面形成有：无色透明的厚度为0.5～20nm，且由30～50原子.％的O、5～15原子％的P以及余量实质Sn构成的保护膜，而且，与接合于基板的半导体元件的形状大致相同。
3.根据权利要求2所述的芯片焊接用软钎料颗粒，其特征在于，
所述芯片焊接用软钎料颗粒的厚度是0.05～1mm。
4.根据权利要求2及3所述的芯片焊接用软钎料颗粒，其特征在于，
所述Sn为主成分的无铅软钎料合金是Sn系合金、Sn-Cu系合金、Sn-Ag系合金、Sn-Ag-Cu系合金、Sn-Bi系合金、Sn-Pb系合金的任一种。
5.一种芯片焊接用软钎料颗粒，其接合电子零件的半导体元件和基板，其特征在于，
该颗粒是如下一种颗粒，即，在软钎焊加热时，在Sn为主成分的无铅软钎料合金的表面形成有：无色透明的厚度为0.5～20nm，且由10～30原子％的In、40～60原子.％的O、5～15原子％的P以及余量实质Sn构成的保护膜，而且，与接合于基板的半导体元件的形状大致相同。
6.根据权利要求5所述的芯片焊接用软钎料颗粒，其特征在于，
所述芯片焊接用软钎料颗粒的厚度是0.05～1mm。
7.根据权利要求5及6所述的芯片焊接用软钎料颗粒，其特征在于，
所述Sn为主成分的无铅软钎料合金是Sn-In系合金、Sn-Bi-In系合金的任一种。
8.一种芯片焊接用软钎料颗粒的制造方法，是权利要求2～4所述的芯片焊接用软钎料颗粒的制造方法，其特征在于，
在将由0.3～1.0质量％的Cu、0.01～0.1质量％的Ni、0.0001～0.02质量％的P、以及余量实质为Sn构成的软钎料合金成形为颗粒状之后，在氧浓度50PPM以下的氢氮气氛中，在235℃以上加热3分钟并加热到峰值温度280℃，形成保护膜。
9.一种芯片焊接用软钎料颗粒的制造方法，是权利要求2～4所述的芯片焊接用软钎料颗粒的制造方法，其特征在于，
在将由3.0～4.0质量％的Ag、0.3～1.0质量％的Cu、0.01～0.1质量％的Ni、0.0001～0.02质量％的P、以及余量实质为Sn构成的软钎料合金成形为颗粒状之后，在氧浓度50PPM以下的氢氮气氛中，在235℃以上加热3分钟并加热到峰值温度280℃，形成保护膜。
10.一种芯片焊接用软钎料颗粒的制造方法，是权利要求5～7所述的芯片焊接用软钎料颗粒的制造方法，其特征在于，
在将由0.2～2.0质量％的In、0.0001～0.02质量％的P、以及余量实质为Sn构成的软钎料合金成形为颗粒状之后，在氧浓度50PPM以下的氢氮气氛中，在235℃以上加热3分钟并加热到峰值温度280℃，形成保护膜。
11.一种电子零件，其特征在于，
利用如下所述的合金对半导体元件和基板进行芯片焊接接合，而且该接合面的空隙率在10％以下，所述合金是在软钎焊过热时，在Sn为主成分的无铅软钎料合金的表面形成：无色透明的由30～50原子.％的O、5～15原子％的P及余量实质Sn构成的保护膜；以及由10～30原子％的In、40～60原子.％的O、5～15原子％的P及余量实质Sn构成的保护膜。
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EP1783827A1 (en) 2007-05-09
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JP2011249839A (ja) 2011-12-08
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US20080246164A1 (en) 2008-10-09
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