CN110914472A - 键合基板和保护用于引线键合的表面的方法 - Google Patents

键合基板和保护用于引线键合的表面的方法 Download PDF

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Publication number
CN110914472A
CN110914472A CN201880041322.7A CN201880041322A CN110914472A CN 110914472 A CN110914472 A CN 110914472A CN 201880041322 A CN201880041322 A CN 201880041322A CN 110914472 A CN110914472 A CN 110914472A
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weight
corrosion inhibitor
inhibitor layer
copper
bonding
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约阿希姆·甘茨
乌维·德赖西希阿克
伊莎贝尔·布雷施
鲍里斯·米泽科夫
德尔维希·土尔库曼
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SOLUTIONS Ltd
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SOLUTIONS Ltd
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    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
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    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
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    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Wire Bonding (AREA)
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Abstract

公开了一种键合基板，其具有由铜或铜基合金制成的用于键合导线(5)的接触焊盘(4a)，该接触焊盘(4a)覆盖有包含含氮的脂烃作为活性物质以及含氮的杂环芳香族化合物作为另一活性物质的腐蚀抑制剂层。根据本发明，在不含水分的情况下，腐蚀抑制剂层含有5％重量或更多的脲衍生物，或3％重量或更多的三苯基胍，或2％重量或更多的四唑衍生物，或5％重量或更多的1‑H‑苯并三唑，或5％重量或更多的苯并咪唑。另外，公开了一种具有这种键合基板的电子模块，以及防止由铜或铜基合金制成的用于引线键合的表面免于腐蚀的方法。

Description

键合基板和保护用于引线键合的表面的方法
技术领域
本发明涉及具有由铜或铜基合金制成的表面的键合基板，并且涉及一种保护用于引线键合的由铜或铜基合金制成的表面的方法。
背景技术
从WO2014/027566A1中已知了具有由权利要求1的前序部分所限定的特征的键合基板。
键合基板具有由铜或铜基合金制成的接触焊盘，其设置用于键合由铜或铜基合金制成的导线。在键合期间，将导线焊接到接触焊盘的铜或铜基合金上。有多种方法常用于这一目的，例如热压键合、热超声球楔键合和超声楔-楔键合。
由铜或铜基合金制成的表面容易腐蚀，铜表面上的氧化层可能会造成导线与表面的键合困难，甚至阻止导线与表面的键合。铜表面可涂覆有铝、铝硅合金、银或其他耐腐蚀金属，以保护键合基板或其用于键合的接触焊盘。然而，已知的镀覆方法会导致相当大的费用。
WO2016/124382A1公开了通过含有丙烯酸酯聚合物的漆来保护铝-铜复合半成品免于腐蚀。但是，这种丙烯酸酯聚合物必须在键合之前除去，因此会造成相当大的花费。
发明内容
本发明的一个目的是展示出如何能够以较少的花费来保护打算用于引线键合的铜或铜基合金的表面免受腐蚀，而无需在键合之前采用单独的操作来去除保护层。
根据本发明，该目的通过有机腐蚀抑制剂层来实现，该有机腐蚀抑制剂层施加到铜表面或铜基合金的表面上，并包含含氮的脂肪烃作为活性物质。脂肪烃也可简称为脂烃(aliphates)。含有杂原子的脂烃，特别是含氮和/或含硫的脂烃可通过范德华力很好地粘附在铜表面上，并且具有氧化抑制作用，特别是当使用含氮的脂烃时，其具有还原作用。这样，键合基板的接触焊盘可以有效且低成本地防止腐蚀。
在根据本发明的方法中，腐蚀抑制剂层作为液体层，即作为水溶液来施加。液体层然后例如可以通过干燥来形成固体的腐蚀抑制剂层，或者液体层可以保持液体，即形成液体的腐蚀抑制剂层。在所施加的溶液干燥之后或期间，包含在其中的组分可以交联，即形成聚合物层。
在根据本发明的腐蚀抑制剂层中的含有杂原子的脂烃例如可以是脲衍生物或胍衍生物，例如三苯基胍。在没有任何水分的情况下，腐蚀抑制剂层优选包含至少20％重量，更优选至少40％重量的含氮脂烃。在下文中，以％重量计的数据是指没有任何水分的腐蚀抑制剂层，即其干质量。
根据本发明，腐蚀抑制剂层含有作为另一活性物质的含氮的杂环芳族化合物，例如四唑和/或三唑衍生物。作为替代或附加，例如可以使用苯胺衍生物和异氰酸根合苯作为含氮的杂环芳族化合物。杂环芳族化合物由于其包含杂原子(例如氮或硫)和碳原子的芳环而具有自由电子对，该自由电子对允许对金属表面的特别良好的粘附。
根据本发明的另一有利的改进方案，腐蚀抑制剂层中的一种或多种含氮的活性物质还包含硫。例如，异硫氰酸根合苯可用作这种活性物质。
腐蚀抑制剂层的有效成分例如可以是脲衍生物和/或苯胺衍生物，优选与四唑衍生物相结合。作为替代或附加，腐蚀抑制剂层可包含三苯基胍和/或苯基脲和/或异硫氰酸根合苯和/或四唑衍生物作为有效成分。腐蚀抑制剂层可以水溶液的形式施加，其中有效成分例如可具有2至10％重量的含量。特别合适的四唑衍生物尤其为1-苯基-1H-四唑-5-硫醇和/或1-苯基-1H-四唑-5-硫醇钠，优选地在pH值为9至12的溶液中。
在没有水分的情况下，腐蚀抑制剂层优选包含至少10％重量，更优选至少30％重量的一种或多种脲衍生物和一种或多种苯胺衍生物以及一种或多种四唑衍生物和/或三苯基胍和/或苯基脲和/或异硫氰酸根合苯和/或四唑衍生物。在没有水分的情况下，腐蚀抑制剂层特别优选地主要由一种或多种脲衍生物和一种或多种苯胺衍生物和/或三苯基胍和/或苯基脲和/或异硫氰酸根合苯和一种或多种四唑衍生物组成。
以下重量份均是指不含水分的腐蚀抑制剂层。当施加时，腐蚀抑制剂层可具有显著量的水分，例如50％重量到95％重量。
例如，腐蚀抑制剂层可包含5％重量或更多，优选20％重量或更多，更优选30％重量或更多的脲衍生物。
作为替代或附加，腐蚀抑制剂层可包含5％重量或更多，优选20％重量或更多，更优选30％重量或更多的苯胺衍生物。
作为替代或附加，腐蚀抑制剂层可包含3％重量或更多，优选20％重量或更多，更优选30％重量或更多的三苯基胍。
作为替代或附加，腐蚀抑制剂层可包含5％重量或更多，优选20％重量或更多，更优选30％重量或更多的苯脲。
作为替代或附加，腐蚀抑制剂层可包含10％重量或更多，优选20％重量或更多，更优选30％重量或更多的异硫氰酸根合苯。
作为替代或附加，腐蚀抑制剂层可以包含5％重量或10％重量或更多，优选10％重量或更多的四唑衍生物。优选地，腐蚀抑制剂层包含不超过30％重量的四唑衍生物。
腐蚀抑制剂层可以低成本地以液体形式施用并形成薄层，从而不必在键合之前将其除去。优选地，腐蚀抑制剂层的厚度不大于400nm。然而，即使最大厚度为100nm或更小的腐蚀抑制剂层也足以进行有效的腐蚀防护，例如，厚度不超过50nm的腐蚀抑制剂层。通常来说，10nm的厚度就足够了，只有很少的情况需要30nm或更大的厚度来用于有效的腐蚀防护。
作为替代或附加，腐蚀抑制剂层可包含1-H-苯并三唑和/或苯并咪唑和/或磷酸盐作为有效成分。另外，腐蚀抑制剂层可包含有机和/或无机酸，例如磷酸盐和/或硫酸。在没有任何水分的情况下，腐蚀抑制剂层例如可含有1％重量或更多的磷酸盐，约5％重量或更多的磷酸盐。以这种方式，可以实现酸性的腐蚀抑制剂层，其优选具有4.0或更小的pH值，特别是3.5或更小的pH值，例如3.0或更小的pH值。然而，腐蚀抑制剂层也可以是弱酸性的、中性的或弱碱性的，例如通过包含苯并咪唑和/或乙二醇异丙醚和/或苯胺和/或异硫氰酸根合苯和/或1-H-苯并三唑和/或双酚A乙氧基化物作为有效成分。在这种情况下，例如pH值为4至8可能是有利的。
根据本发明的一种有利的改进方案，腐蚀抑制剂层包含至少10％重量的1-H-苯并三唑和/或苯并咪唑，优选至少20％重量的1-H-苯并三唑和/或苯并咪唑，其中这些规格是指不含水分的腐蚀抑制剂层。当腐蚀抑制剂层包含水分时，基于总重量的1-H-苯并三唑和/或苯并咪唑的含量因此可以更低。
键合基板可以形成为主体，其被适当地插入到框架中，该框架通过注射成型形成，例如，键合基板可以是冲压件或嵌件。该主体的一部分表面形成接触焊盘，也就是说，它用于键合导线。这样的键合基板通常具有图案化的引线框架，然后将其放置在适合于该目的的框架的隔室中，从而暴露出接触焊盘。然而，根据本发明的腐蚀抑制剂层可以用于保护铜或铜基合金的表面，其设置用于键合导线，并因此形成任意形状的键合基板的接触焊盘。
附图说明
下面参考本发明的实施例来说明本发明的更多细节和优点。
图1示出了具有框架的电子模块的一部分，其中，键合基板的隔室中布置有接触焊盘。
具体实施方式
图1示出了电子模块1的一部分，该电子模块1具有带有隔室3的框架2。在一些隔室3中布置有键合基板4，该键合基板可具有H形的横截面。键合基板4具有接触焊盘4a，其接合线5被固定并引向印刷电路板6。
键合基板4的接触焊盘4a由铜或铜基合金(例如CuNi3SiMg)制成，因此易于腐蚀。因此，在键合基板4或至少其接触焊盘4a制成之后，用有机腐蚀抑制剂层来涂覆它们。
腐蚀抑制剂层以水溶液形式来施加，例如通过浸渍或喷涂。在施加之后，腐蚀抑制剂层会流失水分，变成固体层或保持为液体层。
例如，1-H-苯并三唑和/或苯并咪唑的酸性水溶液可作为腐蚀抑制剂层。这种溶液的pH值优选低于4.0，例如低于3.5，或甚至低于3.0。溶液优选地包含一种或多种无机酸，例如磷酸和/或硫酸。另外，这样的腐蚀抑制剂层优选包含例如1％重量或更多的磷酸盐。例如，将10ml的1-H-苯并三唑和/或10ml的苯并咪唑与1升的水混合，然后施加以产生这样的腐蚀抑制剂层。例如，可以向该混合物中添加10ml的无机酸(例如磷酸或硫酸)，除了酸以外，还可以将磷酸盐(例如1至10mg的磷钼酸铵)溶解其中。
这样的腐蚀抑制剂层对300μm的铜线与CuNi3SiMg的键合基板表面的键合性以及对从其中冲压得到的引线框表面没有负面影响。
例如，由1-苯基-1H-四唑-5-硫醇和/或1-苯基-1H-四唑-5-硫醇钠与脲衍生物和/或苯胺衍生物和/或三苯基胍相结合组成的腐蚀抑制剂也可用于腐蚀抑制剂层，其中该腐蚀抑制剂层优选地还包含苯基脲和异硫氰酸根合苯。为此，例如将20毫升这样的腐蚀抑制剂与1升水混合，然后将该水溶液施加到键合基板4上。该溶液可以在键合基板上干燥，并通过交联形成固体层。
例如，可以通过将10毫克的1-苯基-1-H-四唑-5-硫醇、10毫克的1-苯基-1H-四唑-5-硫醇钠、10毫克的一种或多种脲衍生物、10毫克的一种或多种苯胺衍生物、10毫克的三苯基胍、10毫克的苯基脲和10毫克的异硫氰酸根合苯混合，并向该混合物中加入1升水来得到腐蚀抑制剂层。
另一可能性在于使用苯并咪唑和乙二醇异丙醚作为腐蚀抑制剂。或者，苯胺和/或异硫氰酸根合苯和/或1-H-苯并三唑可以分别与双酚A聚氧乙烯醚组合使用，其中可以加入酸，例如有机酸，例如乙酸。可以将100毫升至200毫升的这种腐蚀抑制剂与1升水混合，然后以水溶液的形式施加到键合基板上。
附图标记列表
1 电子模块
2 框架
3 隔室
4 键合基板
4a 接触焊盘
5 导线
6印刷电路板

Claims (14)

1.一种键合基板，包括由铜或铜基合金制成的用于键合导线(5)的接触焊盘(4a)，
所述接触焊盘(4a)覆盖有腐蚀抑制剂层，其包含含氮的脂烃作为活性物质，以及含氮的杂环芳香族化合物作为另一活性物质，
其特征在于，在不含水分的情况下，所述腐蚀抑制剂层含有
5％重量或更多的脲衍生物，或
3％重量或更多的三苯基胍，或
2％重量或更多的四唑衍生物，或
5％重量或更多的1-H-苯并三唑，或
5％重量或更多的苯并咪唑。
2.根据权利要求1所述的键合基板，其特征在于，所述腐蚀抑制剂层含有比杂环芳族化合物更多的脂烃。
3.根据上述权利要求中任一项所述的键合基板，其特征在于，在不含水分的情况下，所述腐蚀抑制剂层由至少10％重量的一种或多种以下物质组成：脲衍生物、苯胺衍生物、三苯基胍、苯基脲、异硫氰酸根合苯和/或四唑衍生物。
4.根据上述权利要求中任一项所述的键合基板，其特征在于，在不含水分的情况下，所述腐蚀抑制剂层包含至少10％重量的四唑衍生物。
5.根据上述权利要求中任一项所述的键合基板，其特征在于，所述四唑衍生物是1-苯基-1H-四唑-5-硫醇和/或1-苯基-1H-四唑-5-硫醇钠。
6.根据上述权利要求中任一项所述的键合基板，其特征在于，在不含水分的情况下，所述腐蚀抑制剂层包含至少8％重量的1-H-苯并三唑和/或苯并咪唑。
7.根据权利要求1到6中任一项所述的键合基板，其特征在于，所述腐蚀抑制剂层的pH值小于4.0。
8.根据权利要求1至5中任一项所述的键合基板，其特征在于，所述腐蚀抑制剂层的pH值为9至12。
9.根据权利要求7或8所述的键合基板，其特征在于，在不含水分的情况下，所述腐蚀抑制剂层包含至少1％重量的磷酸盐。
10.根据上述权利要求中任一项所述的键合基板，其特征在于，在不含水分的情况下，所述腐蚀抑制剂层由至少10％重量的一种或多种以下物质组成：苯并咪唑、乙二醇异丙醚、苯胺、异硫氰酸根合苯、1-H-苯并三唑和双酚A聚氧乙烯醚。
11.根据上述权利要求中任一项所述的键合基板，其特征在于，所述腐蚀抑制剂层的厚度不大于400nm。
12.一种电子模块，具有框架(2)，所述框架具有隔室(3)，在所述隔室中布置有根据上述权利要求中任一项所述的键合基板(4)。
13.一种用于保护由铜或或铜基合金制成的提供用于引线键合的表面免受腐蚀的方法，其特征在于，所述表面覆盖有有机腐蚀抑制剂层，所述有机腐蚀抑制剂层包含含氮的脂烃作为活性物质，以及含氮的杂环芳香族化合物作为另一活性物质层，其中，在不含水分的情况下，所述腐蚀抑制剂层含有5％重量或更多的脲衍生物，或3％重量或更多的三苯基胍，或2％重量或更多的四唑衍生物，或5％重量或更多的1-H-苯并三唑，或5％重量或更多的苯并咪唑。
14.根据权利要求13所述的方法，其特征在于，所述腐蚀抑制剂层以水溶液形式来施加。
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