CN104882429A - 用于非贵金属接合搭接垫的薄NiB或CoB封盖层 - Google Patents

用于非贵金属接合搭接垫的薄NiB或CoB封盖层 Download PDF

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Publication number
CN104882429A
CN104882429A CN201510093579.5A CN201510093579A CN104882429A CN 104882429 A CN104882429 A CN 104882429A CN 201510093579 A CN201510093579 A CN 201510093579A CN 104882429 A CN104882429 A CN 104882429A
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Prior art keywords
base metal
joint pad
capping layer
substrate
metal joint
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CN201510093579.5A
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CN104882429B (zh
Inventor
E·贝内
J·德沃斯
J·德拉克山得
L·英格兰
G·瓦喀纳斯
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Interuniversitair Microelektronica Centrum vzw IMEC
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Interuniversitair Microelektronica Centrum vzw IMEC
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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Abstract

本发明涉及一种基板，该基板具有至少一个主表面，所述主表面包括被封盖层覆盖的至少一个非贵金属接合搭接垫，从而将非贵金属接合搭接垫从环境掩蔽开来。该封盖层包括合金，合金是NiB或CoB并且含有原子浓度百分率为10-50％的硼。

Description

用于非贵金属接合搭接垫的薄NiB或CoB封盖层
领域
本发明涉及覆盖基板上非贵金属接合垫的封盖层。
背景技术
开发了采用接合结构的新技术，由此热-压制接合(TCB)的使用变得更为普及。例如，TCB可用于引线接合、倒装芯片(Flip Chip)接合或芯片堆叠。它需要凸出的触点，例如由Au或Cu引线或含Sn基焊料触头的Cu柱形成的钉头凸点。这些凸出的触点可位于基板上或者在接合结构的另一组件上。在凸出的触点的相对面，平坦的触点(优选与凸出的触点是相同材料)用作接合部件，称为接合搭接垫。该材料可以是非贵金属。
TCB工艺通过在需要接合的两种组件上应用压力方案和热方案实现了接合结构的两种组件之间的最终接合。通常，TCB工艺期间两种组件之间存在底部填充材料。
通常，在它们接合之前，接合结构中需要接合的组件的制造期间存在储存时间。还应注意，组装工艺本身以及储存不一定是在非氧化环境中。这些因素最终可能导致非贵金属接合搭接垫的氧化。众所周知的事实是，非贵金属接合搭接垫的氧化常常导致接合工艺期间焊点形成问题。当底部填充材料的熔解能力不足以去除接合工艺期间的非贵金属氧化物时尤其是这样。
利用无电沉积(ELD)厚(>0.5μm)的NiP、低(最高至5重量％)硼含量的NiB、Au、Pd或其堆叠组合来涂覆或封盖金属接合搭接垫，以防止金属接合搭接垫的氧化。例子参见US 7,078,796B2。这些解决方案需要具有优异非氧化性质的贵金属如Au或Pd，但是这些材料非常昂贵。这些贵金属具有优异的抗氧化性，但它们是稀有材料并且昂贵。本发明的目的是用常规可得的较便宜的替代品代替这些材料。
附图简要说明
图1a,b,c,d显示了根据本发明第一方面可能的实现形式，其中封盖层完全覆盖非贵金属接合搭接垫。
图2a,b,c显示了根据本发明第二方面可能的实现形式，其中封盖层部分覆盖非贵金属接合搭接垫。
图3显示了根据本发明的实施方式，对于不同厚度的NiB封盖层的Cu-氧化物和NiB氧化物的表面浓度(原子百分率:At％)。
图4显示了根据本发明的实施方式，对于不同厚度的NiB封盖层的接触菊链的产率。
详细描述
将就具体实施方式并参照某些附图对本发明进行描述，但本发明并不受此限制。所述附图仅为示意性而不具限制性。在附图中，为达到说明的目的，可能放大一些元件的尺寸而未按比例绘制。所述尺寸和相对尺寸不必然对应于本发明付诸实施的实际情况。
另外，在说明书以及权利要求书中，术语“第一”、“第二”和“第三”等仅仅是用来区别类似的元件，而不是用来描述次序或时间顺序。在适当的情况下，这些术语可互换，且本发明的实施方式可以如本文所述和所示以外的其它顺序操作。
此外，在说明书和权利要求书中，术语“顶部”、“底部”、“上方”、“下方”等用于描述目的，而不一定用于描述相对位置。在适当的情况下，这些术语可互换，且本发明的实施方式可以如本文所述和所示以外的其它顺序操作。
应注意，权利要求书中使用的术语“包含”不应解释为被限制为其后列出的技术手段，其不排除其它元件或步骤。因此应将其解释为详细说明存在所提到的所述特征、整数、步骤或组分，但不排除存在或添加一个或多个其它特征、整数、步骤或组分或其组合。因此，“包含技术手段A和B的装置”表述的范围不应限于仅由组件A和B组成的装置。其表示就本发明而言，所述装置仅有的相关组件是A和B。
图1a显示了根据本发明的第一方面的基板1，所述基板具有至少一个主表面11，主表面包括至少一个非贵金属接合搭接垫2，该非贵金属接合搭接垫被封盖层3覆盖，将非贵金属接合搭接垫2从环境掩蔽开来。该封盖层3包括合金，合金是NiB或CoB并且含有原子浓度百分率为10-50％的硼。
图1b-1c显示了本发明第一方面的其他替代实现形式。应理解，这些替代实现形式也是可能的。
图1a,b,c,d的基板1可选自以下列表：半导体基板、印刷电路板、玻璃面板、弹性基板、重建晶片或主表面11上包括非贵金属接合搭接垫2的任何基材。半导体基板可包括至少一个半导体装置和互连结构，该至少一个半导体装置通过至少部分互连结构与非贵金属接合搭接垫电连接。基板1可包括至少两个接合管芯的堆叠，至少一个接合管芯在内插件基板上的堆叠或者至少一个接合管芯在晶片上的堆叠。
图1a,b,c,d中基板1的主表面11是平坦表面，在该表面上发生接合，例如“在硅内插件基板上的倒装芯片热压制接合”。注意该主表面可以是基板的顶部或者底部平坦表面11或者是两者。
图1a,b,c,d中的非贵金属接合搭接垫2被构造成接合工艺中的接收实体。通常，出于本领域众所周知的各种原因，例如应力缓解、底部填充分配F分配或者熔解，两个实体或组件之间需要一些基准距高度(stand-offheight)。接合工艺中的非接收实体通常具有接合材料，而接收实体具有搭接垫以容纳接合工艺期间的接合材料。接合材料可以是但不限于：焊料、接合线、金属柱等。
涉及本发明第一方面的非贵金属接合搭接垫2并不排斥贵金属如Au和Pd。这些贵金属具有优异的抗氧化性质，但是是稀有材料并且昂贵。本发明的目的是用常规可得的较便宜的替代品代替这些材料。
由于非贵金属接合搭接垫2不含贵金属接合层，所以需要封盖层3以避免非贵金属接合搭接垫2的氧化。封盖层3覆盖非贵金属接合搭接垫2，从而将非贵金属接合搭接垫2从氧化环境掩蔽开来。注意被封盖层3覆盖的金属接合搭接垫与该封盖层3直接接触。
环境可包括氧，即使是少量(例如低到30ppm)也将导致非贵金属的氧化。即使在焊接期间采用氮气环境和/或流体汽相气氛的工具中也可能发生氧化，因为在这些环境中氧分压仍然显著并且因此导致非贵金属接合搭接垫2的氧化。非贵金属接合搭接垫的氧化可能在储存期间或者在接合设施或者含有这种金属接合搭接垫的基板的组装车间发生。封盖层3起到扩散阻挡层的作用，防止氧从环境穿过封盖层3而到达非贵金属接合搭接垫2的非贵金属。反过来，封盖层3也能防止金属从非贵金属接合搭接垫2向外穿过封盖层3扩散而到达环境，在环境中遇氧而易于氧化。
众所周知的是，非贵金属接合搭接垫2的氧化可导致劣质接合，必须加以避免，以维持高接合率、优良的接合可靠性和接合结构的成本效率。
意外地发现，采用含有原子浓度百分率为10-50％的B的NiB或CoB合金作为覆盖非贵金属接合搭接垫2的封盖层3产生优异的扩散阻挡性质，有效防止扩散通过封盖层，因而防止被封盖层3覆盖的非贵金属接合搭接垫2中非贵金属的氧化。
意外地发现，根据本发明的第一方面，采用含有原子浓度百分率为10-50％的B的NiB或CoB合金作为覆盖非贵金属接合搭接垫2的封盖层3，使非贵金属接合搭接垫2被封盖层覆盖的部分具有优异的浸润性质，能够与常规焊料如Sn实现优良可焊性。
意外地发现，根据本发明的第一方面，采用含有原子浓度百分率为10-50％的B的NiB或CoB合金作为覆盖非贵金属接合搭接垫2的封盖层3，该垫2在接触含有氧的正常空气环境时不易氧化。目前相信这可能是因为NiB或CoB合金中高原子浓度百分率的B，B用作Ni或Co金属中的填隙元素，从而防止封盖层3中存在的Ni或Co的氧化。B在物理尺寸方面足够小，以匹配进入Ni或Co晶格中的空间。这样，NiB或CoB具有与贵金属一样的性质，但成本降低。发现更低原子浓度百分率的B不足以防止NiB或CoB的氧化。相信这与Ni或Co晶格中的空缺有关，这些空缺仍然存在，从而使得环境中的氧能够氧化Ni或Co。
意外地发现，根据本发明的第一方面，采用含有原子浓度百分率为10-50％的B的NiB或CoB合金作为覆盖非贵金属接合搭接垫2的封盖层3，该垫在接触含有H2O的正常环境时不易腐蚀。目前相信这可能是因为NiB或CoB合金中高原子浓度百分率的B，B用作Ni或Co金属中的填隙元素，从而防止封盖层3中Ni或Co的腐蚀。B在物理尺寸方面足够小，以匹配进入Ni或Co晶格中的空间。这样，NiB或CoB像贵金属一样有效，但成本降低。发现更低原子浓度百分率的B不足以防止NiB或CoB的腐蚀。相信这与Ni或Co晶格中的空缺有关，这些空缺仍然存在，从而使得H2O能够腐蚀Ni或Co。
意外地发现，根据本发明的第一方面，采用含有原子浓度百分率为10-50％的B的NiB或CoB合金作为覆盖非贵金属接合搭接垫2的封盖层3，获得硬质且光滑的封盖层的外表面，防止封盖层3在诸如探针测试期间受到损坏。根据本发明实施方式的基板1通常通过探针进行测试，将探针抵靠接合搭接垫按压以在生产测试期间建立电接触，检查基板1在接合之前或者组装过程期间是否起作用。这种事前的测试避免错误基板被昂贵的接合实体填充。因此，需要探针测试来控制成本。封盖层3硬度提高的另一个优点是，与贵金属或未封盖的非贵金属接合搭接垫相比，采用压制型接合时接合工艺中的压力降低。这可改善接合的可制造性，因为较低的压力表明位于非贵金属接合搭接垫2附近的装置受损风险降低，因为这些装置需要承受接合工艺期间施加的局部压力。封盖层的硬度通常随着B原子浓度的增加而增加。最小的厚度确保均一的封盖层具有包括硬度在内的均一性质。
本发明第一方面的封盖层的优点在于，单一的封盖层3将需要的功能如扩散阻挡性质、建立非氧化封盖层、增加的硬度、易得、便宜和具有优良的润湿性质结合起来。由于这些非氧化性质，这具有成本优势以及性能优势。
根据本发明第一方面的B原子浓度百分率的上限是50％。这对应于Ni1B1或Co1B1。因此，在上限中，完整的封盖层3由Ni1B1或Co1B1构成。在较低的浓度，形成其他硼化物，例如Ni3B，这对应于B原子浓度百分率25％。封盖层3的最终组成是金属Ni和Ni硼化物的混合物，或者金属Co与Co硼化物的混合物，取决于封盖层所用材料。
在一个实施方式中，封盖层3的厚度大于9nm且小于50nm。降低覆盖非贵金属接合搭接垫2的封盖层3的厚度还能够按比例缩小(例如但不限于)倒装芯片组装期间热压制接合中使用的微凸块。应注意，所揭示的封盖层3的厚度范围要比例如Au或Pd封盖层通常施加的厚度小得多。显然这对于目前和未来缩放是有利的。较薄的封盖层3也能实现制造期间较短的沉积时间和较高的通量。发现需要厚度大于9nm的封盖层3以实现覆盖非贵金属接合搭接垫2的封盖层3的均一厚度。上限是为了限定最终接合中封盖层3材料的量。对于引线接合，无需厚的封盖层3。更厚的封盖层需要更多时间沉积。最优选地，用于热压制接合的封盖层的厚度为15-25nm。最优选地，用于引线接合的封盖层3的厚度为9-15nm。
在一个实施方式中，非贵金属接合搭接垫2包含Cu,Co,Ni,Mo或Mn。这些材料是非贵金属并且在基板制造工业中具有已知的优点，因此与现有技术的基础设施相容。此外，它们具有优良的电和热传导性，因此最终的接合在接合实体之间产生优良的电和热连接。它们还向封盖层3提供优良的粘合性。
如图2a所示，第二方面涉及一种基板1，所述基板具有至少一个主表面11，主表面包括至少一个非贵金属接合搭接垫2，该非贵金属接合搭接垫被封盖层部分覆盖，将非贵金属接合搭接垫2的被覆盖部分12从环境掩蔽开来。该封盖层3包括合金，合金是NiB或CoB并且含有原子百分率为10-50％的硼。
图2a-2b显示了本发明第二方面的替代实现形式。应理解，其他替代实现形式也是可能的。
图2a,b,c的基板1可选自以下列表：半导体基板、印刷电路板、玻璃面板、弹性基板或主表面11上包括非贵金属接合搭接垫2的任何基材。半导体基板可包括至少一个半导体装置和互连结构，该至少一个半导体装置通过至少部分互连结构与非贵金属接合搭接垫电连接。基板1可包括至少两个接合管芯的堆叠，至少一个接合管芯在内插件基板上的堆叠，或者至少一个接合管芯在晶片上的堆叠。
图2a,b中基板1的主表面11是平坦表面。在该表面上发生接合，例如“在硅内插件基板上的倒装芯片热压制接合”。注意该主表面可以是基板的顶部或者底部平坦表面11或者是两者。
图2a,b,c中的非贵金属接合搭接垫2被构造成接合工艺中的接收实体。通常，出于本领域众所周知的各种原因，例如应力缓解、底部填充分配或者熔解，两个实体之间需要一些基准距高度。接合工艺中的非接收实体通常具有接合材料，而接收实体具有搭接垫以容纳接合工艺期间的接合材料。接合材料可以是但不限于：焊料、接合线、金属柱等。
非贵金属接合搭接垫2并不排斥贵金属如Au和Pd。这些贵金属具有优异的抗氧化性质，但是是稀有材料并且昂贵。本发明的目的是用常规可得的较便宜的替代品代替这些材料。
由于非贵金属接合搭接垫2不含贵金属接合层，所以需要封盖层3以避免非贵金属接合搭接垫2的氧化。封盖层3部分覆盖非贵金属接合搭接垫2，从而在垫上发生接合的位置将非贵金属接合搭接垫2从环境掩蔽开来。注意被封盖层3覆盖的金属接合搭接垫与该封盖层3直接接触。非贵金属接合垫2没有被封盖层3覆盖的部分没有从环境掩蔽开，因此暴露于环境。
含氧环境，即使小到30ppm的少量，也可导致非贵金属的氧化。即使在焊接期间采用氮气环境和/或流体汽相气氛的工具中也可能发生氧化，因为在这些环境中氧分压仍然显著并且因此导致非贵金属接合搭接垫2的氧化。氧化可能在储存期间或者在接合设施或者组装车间发生。封盖层3起到扩散阻挡层的作用，防止氧从环境穿过封盖层3而到达非贵金属接合搭接垫2的非贵金属。反过来，封盖层3也能防止金属从非贵金属接合搭接垫2向外穿过封盖层3扩散而到达环境，在环境中遇氧而易于氧化。
众所周知的是，非贵金属接合搭接垫2的氧化可导致劣质接合，因此必须加以避免，以维持高接合率、优良的接合可靠性和接合结构的成本效率。
意外地发现，采用含有原子浓度百分率为10-50％的B的NiB或CoB合金作为部分覆盖非贵金属接合搭接垫2的封盖层3产生优异的扩散阻挡性质，有效防止扩散通过封盖层并因而防止被封盖层3覆盖的非贵金属接合搭接垫2中非贵金属的氧化。
意外地发现，采用含有原子浓度百分率为10-50％的B的NiB或CoB合金作为部分覆盖非贵金属接合搭接垫2的封盖层3，使非贵金属接合搭接垫2被封盖层部分覆盖的部分具有优异的浸润性质，能够与已知焊料如Sn实现优良可焊性。
意外地发现，采用含有原子浓度百分率为10-50％的B的NiB或CoB合金作为部分覆盖非贵金属接合搭接垫2的封盖层3，该垫2在接触含有氧的正常空气环境时不易氧化。目前相信这可能是因为NiB或CoB合金中高原子浓度百分率的B，B用作Ni或Co金属中的填隙元素，从而防止封盖层3中Ni或Co的腐蚀。B在物理尺寸方面足够小，以匹配进入Ni或Co晶格中的空间。这样，NiB或CoB像贵金属一样有效，但成本降低。发现更低原子浓度百分率的B不足以防止NiB或CoB的氧化。相信这与Ni或Co晶格中的空缺有关，这些空缺仍然存在，允许氧来氧化Ni或Co。
意外地发现，采用含有原子浓度百分率为10-50％的B的NiB或CoB合金作为部分覆盖非贵金属接合搭接垫2的封盖层3，该垫2在接触含有H2O的正常环境时不易腐蚀。目前相信这是因为NiB或CoB合金中高原子浓度百分率的B，B用作Ni或Co金属中的填隙元素，从而防止封盖层3中Ni或Co的腐蚀。B在物理尺寸方面足够小，以匹配进入Ni或Co晶格中的空间。这样，NiB或CoB像贵金属一样有效，但成本降低。发现更低原子浓度百分率的B不足以防止NiB或CoB的腐蚀。相信这与Ni或Co晶格中的空缺有关，这些空缺仍然存在，从而使得H2O能够腐蚀Ni或Co。
意外地发现，采用含有原子浓度百分率为10-50％的B的NiB或CoB合金作为部分覆盖非贵金属接合搭接垫2的封盖层3，提供封盖层硬质且光滑的表面。这可防止封盖层3在例如探针测试期间受到损伤。基板1通常通过探针进行测试，将探针抵靠接合搭接垫按压以在生产测试期间建立电接触，检查基板1在接合之前或者组装过程期间是否起作用。这种事前的测试避免错误基板被昂贵的接合实体填充。因此，需要探针测试来控制成本。封盖层3硬度提高的另一个优点是，与贵金属或未封盖的非贵金属接合搭接垫相比，采用压制型接合时接合工艺中的压力降低。这可改善接合的可制造性，因为较低的压力表明位于非贵金属接合搭接垫2附近的装置受损风险降低，因为这些装置需要承受接合工艺期间施加的局部压力。封盖层的硬度通常随着B原子浓度的增加而增加。最小的厚度确保均一的封盖层具有包括硬度在内的均一性质。
本发明第二方面的封盖层的优点在于，单一的封盖层3将需要的功能如扩散阻挡性质、建立非氧化封盖层、增加的硬度、易得、便宜和具有优良的润湿性质结合起来。由于这些非氧化性质，这具有成本优势以及性能优势。
根据本发明第二方面的B原子浓度百分率的上限是50％。这对应于Ni1B1或Co1B1。因此，在上限中，完整的封盖层3由Ni1B1或Co1B1构成。在较低的浓度，形成其他硼化物，例如Ni3B，这对应于B原子浓度百分率25％。封盖层3的最终组成是金属Ni和Ni硼化物的混合物，或者金属Co与Co硼化物的混合物，取决于封盖层所用材料。
在一个实施方式中，封盖层3的厚度大于9nm且小于50nm。降低部分覆盖非贵金属接合搭接垫2的封盖层3的厚度还能够按比例缩小(例如但不限于)倒装芯片组装期间热压制接合中使用的微凸块。应注意，封盖层3的厚度要比例如Au或Pd封盖层通常施加的厚度小得多。显然这对于目前和未来缩放是有利的。较薄的封盖层3也能实现制造期间较短的沉积时间和较高的通量。发现需要厚度大于9nm的封盖层3以实现覆盖非贵金属接合搭接垫2的封盖层3的均一厚度。上限是为了限定最终接合中封盖层3材料的量。对于引线接合，无需厚的封盖层3。更厚的封盖层需要更多时间沉积。最优选地，用于热压制接合的封盖层的厚度为15-25nm。最优选地，用于导线接合的封盖层3的厚度为9-15nm。
在一个实施方式中，非贵金属接合搭接垫2包含Cu,Co,Ni,Mo或Mn。这些金属是非贵金属并且在基材制造工业中具有已知的优点。因此它们与现有技术的基础设施是相容的。此外，它们具有优良的电和热传导性，因此最终的接合在接合实体之间产生优良的电和热连接。它们向封盖层3提供优良的粘合性。
在一个实施方式中，非贵金属接合搭接垫2至少部分地延伸高出主表面11，封盖层3仅覆盖非贵金属接合搭接垫2的顶侧13。这是一个具体例子，其中凸出的非贵金属接合搭接垫2延伸高出主表面。这有利于在两个接合实体之间产生基准距高度。非贵金属接合搭接垫2顶侧13上的封盖层3提供了搭接垫，例如通过引线接合实现接合。覆盖非贵金属接合搭接垫2的整个顶侧13可实现最大的接合面积，并且可用于降低相邻的非贵金属接合搭接垫2之间的节距，以便进一步缩放。采用非贵金属接合搭接垫2的整个顶侧13允许两个接合实体之间较大的未对齐偏差。
在一个实施方式中，非贵金属接合搭接垫2至少部分地延伸高出主表面11，封盖层3仅覆盖非贵金属接合搭接垫2的侧壁14。这是一个具体例子，其中非贵金属接合搭接垫2的顶侧13没有被封盖层3覆盖。例如在进行热压制接合之后是这样。热压制接合导致非贵金属接合搭接垫2顶侧13上的封盖层3溶解在焊料中，而非贵金属接合搭接垫2的侧壁14未受影响。一个优点是侧壁14在接合后受到掩蔽与环境隔离，而顶侧13对焊料具有优良的浸润性，因而获得优良的可焊接性。
在一个实施方式中，非贵金属接合搭接垫2至少部分地延伸高出主表面11，封盖层3仅覆盖非贵金属接合搭接垫2的侧壁14。垫2还包括至少部分覆盖非贵金属接合搭接垫2顶侧13的材料层4，该材料层4包括金属互化物和填隙B。这些金属互化物包括非贵金属接合搭接垫2的金属与主焊料金属和Ni或Co的组合。这是一个具体例子，其中非贵金属接合搭接垫2的顶侧13没有被封盖层3覆盖。例如在进行热压制接合之后是这样，热压制接合导致非贵金属接合搭接垫2顶侧13上的封盖层3溶解在焊料中，而侧壁未受影响。热压制接合还在非贵金属接合搭接垫2顶侧13上留下材料层4。该材料层包括填隙B，B原子足够小以匹配在材料层4不同组件的晶格位置之间。材料层还包括由于接合工艺形成的金属互化物，金属互化物是指涉及金属的固态相。在金属互化物中，不同的元素排序至结构中具有独特的局部环境的不同位点。包括在材料层中的金属互化物是非贵金属接合搭接垫2的金属与主焊料金属和Ni或Co的组合。因此可以检测到所有这三种组分，包括封盖层3中使用的Ni或Co。一个优点在于，侧壁在接合后保持从环境掩蔽开来，而顶侧13具有材料层，材料层在焊料和非贵金属接合搭接垫2之间形成优良的电和物理接合。
在一个实施方式中，根据上述实施方式的基板还包括至少部分覆盖非贵金属接合搭接垫2上没有被封盖层3覆盖的部分的材料层4，其中，材料层4包括金属互化物和填隙B。金属互化物包括非贵金属接合搭接垫2的金属与主焊料金属和Ni或Co的组合。这允许接合工艺期间形成的材料层位于非贵金属接合搭接垫2上没有被封盖层3覆盖的的区域。不一定要求非贵金属接合搭接垫2上没有被封盖层3覆盖的区域被材料层4完全覆盖。部分覆盖就足够，因为两个接合实体之间会发生未对齐的情况，以及顶表面没有被材料层完全覆盖。这并不排斥实现优良接合。
在一个实施方式中，主焊料金属选自下组：Sn,Zn,Bi,Pb或In。主焊料金属是焊料中含量最多的金属，因为大多数焊料由包括金属在内的不同材料组成。焊料中最主要的金属即主焊料金属。这些焊料在封盖层上显示优良的浸润性，如本发明第二方面所述。
本发明的第三方面提供了一种制备根据第一或第二方面的基板的方法，其中在基板(1)主表面(11)上形成至少部分地覆盖非贵金属接合搭接垫(2)的封盖层(3)，所述方法包括以下步骤：
-提供基板，在其主表面上具有至少一个非贵金属接合搭接垫(2)，
-清洁基板(1)的主表面(11)，和
-将覆盖层沉积到金属接合搭接垫经清洁的表面上。
封盖层可采用无电沉积(ELD)实现沉积。清洁步骤可以用基于有机酸的清洁剂和去离子水(DI)冲洗来进行。ELD电镀可以在LAM ELD2300单晶片工具上进行，通常电镀速率约为1埃/秒。可选地，基板可以用DI冲洗并空气干燥。
第一和第二方面中揭示的基板1是刚性的，包括：一个或多个配线层，使得至少一个非贵金属接合搭接垫2与基板内包括的装置互连。这些装置可包括有源装置(例如，晶体管，二极管)，无源装置或组件(例如，电阻器，电容器，电感器)，MEMS装置(例如，压力传感器，加速计，陀螺仪)。基板1还包括被构造成接触外部组件的至少一个非贵金属垫。这些非贵金属垫可位于基板1的所有表面上(顶面、底面和侧面)。基板1也可包括不同的非贵金属垫之间的配线，配线位于基板1的外表面11上，例如对于PCB互连基板而言没有组件在基板内部。基板1可包括表面金属化图案以及如果不保护的话会发生氧化或腐蚀的非贵金属垫。这些表面金属化图案的常用金属是Cu,Ni和Co。这些表面金属可以高于基板1的主表面11(例如凸块、外加互连)，处于同一水平(例如通过CMP，快速切削等实现的平坦化表面11)，或者低于主表面11(例如基板内存在的内部空穴)。
这种金属表面的至少一个非贵金属接合搭接垫可连接至至少一个电子组件或电子子系统。这些连接可通过焊接、热-压制、超声焊接或接合实现。
在本发明的第三方面，揭示了一种基板1，基板1具有至少一个主表面11，主表面11包括至少一个非贵金属接合搭接垫2，非贵金属接合搭接垫被材料层4覆盖。材料层4包括金属互化物和填隙B，金属互化物包括金属接合搭接垫的金属与主焊接金属和Ni或Co的组合。
基板1包括至少一个非贵金属触点与基板1内存在的装置之间的互连配线。这些装置可包括有源装置(例如，晶体管，二极管)，无源组件(例如，电阻器，电容器，电感器)，MEMS装置(例如，压力传感器，加速计，陀螺仪)。基板1还包括仅在其主表面11上的不同的非贵金属触点之间的配线，对于印刷电路板是这样。基板1包括在至少一个主表面11上的表面金属和如果不受保护的话会发生氧化或腐蚀的非贵金属接触垫。这些表面金属的常用材料是Cu,Ni和Co。这些金属可以高于基板表面11(例如凸块、外加互连)，处于同一水平(例如通过CMP，快速切削实现的平坦化表面)，或者低于基板1的主表面11(例如基板内存在的内部空穴)。与该金属表面相关的至少一个非贵金属接触垫将与其他电子组件或电子子系统的非贵金属触点连接。这些连接可通过焊接、热-压制、超声焊接或接合实现。
本发明涉及利用10-50nm厚的无电镀沉积NiB或CoB封盖层3，其中原子B浓度为10-50％，选择性沉积在倾向于氧化和腐蚀的暴露表面金属上，从而防止该表面金属的氧化和/或腐蚀。该保护作用无需沉积额外的保护层(例如传统上使用的贵金属Pd和Au)即可实现。该薄层封盖层3具有以下功能：
-钝化:避免所有暴露的金属表面的氧化和腐蚀(跟踪器，垫)。
-焊接:由于焊料与封盖层3的NiB或CoB表面具有优良的浸润性，可以实现成功焊接。焊接期间，该封盖层3将溶解在焊料中或者转变成金属互化物。这允许焊料和下面的未氧化金属之间的相互作用和金属互化物的形成。(焊接是通过两种材料之间形成金属互化物实现两种金属体的连接，一种材料(焊料)加热至接近其熔点或超过熔点，以实现快速互扩散以及焊料与第二材料体表面材料的合金化)。
-热压制接合：热压制期间，采用机械压力连接两种金属体而不需要熔融。通过利用热和压力，促进界面处材料互扩散以实现两种金属体(也称为接合实体)之间的固相连接。为成功接合，需要干净、非氧化的表面。
-超声接合:接合期间采用超声能量，从而产生表面第一金属元素(例如接合引线(Al,Au,Cu)或金属凸块(Au))与第二元素表面(也称为非贵金属接合搭接垫2)(＝接合垫，暴露的金属表面)之间的密切接触。为成功接合，需要干净、非氧化的金属表面。
-热-超声接合:热压制和超声接合的组合。在热压制期间加入超声能量，用于增强两种连接材料的表面处原子水平上的互相混合。在电子器件中，该方法主要用于金或铜引线接合。
在所有这些应用中，利用薄NiB或CoB封盖层3能够产生：
-不需要贵金属涂层的非氧化表面，用于组装工艺，例如焊接(倒装接合、焊球连接、表面安装组装)；热-压制(倒装芯片)或引线接合(超声或热超声Al,Au或Cu引线)，
-防止装置表面上暴露的金属表面的氧化和腐蚀而不需要保护层等额外的涂层。例如，焊接工艺期间没有被焊料覆盖的金属表面部分或者热-压制或引线接合工艺期间没有被接合材料(凸块或引线)覆盖的金属表面部分。
需要由NiB或CoB封盖层3保护的相关表面金属是：Cu,Ni,Co或Mo。
图3显示了本发明示例性的实施方式。制备测试样品，分别具有5nm,10nm和20nm厚的含30原子％B的NiB封盖层，覆盖Cu接合搭接垫2。然后将这些测试样品在含氧环境中进行0(无回流)至10次的热循环。回流期间，温度高达300℃。然后，采用XPS检查氧化物的存在。图3显示对于NiB试样Cu,Ni和B及其氧化物的浓度。10或20nm厚的NiB层即使在10次回流后明显没有氧化。5nm NiB层不能防止下面的Cu的氧化，尤其是在经历一系列回流时。
图4显示了本发明示例性的实施方式。制备含Cu接触菊链的测试样品，分别具有10nm和16nm厚的含20原子％B的NiB覆盖层3，10nm和20nm厚的含30原子％B的NiB覆盖层3或者没有覆盖层。图4显示了不同菊链的产率。具有NiB封盖层改善了产率。与B浓度相比，NiB封盖层的厚度对产率影响较小。

Claims (12)

1.一种基板(1)，所述基板具有至少一个主表面(11)，所述主表面包括至少一个非贵金属接合搭接垫(2)，所述非贵金属接合搭接垫覆盖有封盖层(3)，从而将所述非贵金属接合搭接垫(2)从环境屏蔽开；其特征在于，所述封盖层(3)包括合金，所述合金是NiB或CoB并且含有原子浓度百分率为10-50％的硼。
2.如权利要求1所述的基板(1)，其特征在于，所述覆盖层(3)的厚度大于9nm且小于50nm。
3.如权利要求1所述的基板(1)，其特征在于，所述非贵金属接合搭接垫(2)含有Cu,Co,Ni,Mo或Mn。
4.一种基板(1)，所述基板具有至少一个主表面(11)，所述主表面包括至少一个非贵金属接合搭接垫(2)，所述非贵金属接合搭接垫部分覆盖有封盖层，从而将所述非贵金属接合搭接垫(2)的覆盖部分(12)从环境屏蔽开；其特征在于，所述封盖层(3)包括合金，所述合金是NiB或CoB并且含有原子浓度百分率为10-50％的硼。
5.如权利要求4所述的基板(1)，其特征在于，所述覆盖层(3)的厚度大于9nm且小于50nm。
6.如权利要求4所述的基板(1)，其特征在于，所述非贵金属接合搭接垫(2)含有Cu,Co,Ni,Mo或Mn。
7.如权利要求4所述的基板(1)，其特征在于，所述非贵金属接合搭接垫(2)至少部分延伸高出所述主表面(11)并且所述封盖层(3)仅覆盖所述非贵金属接合搭接垫(2)的顶侧(13)。
8.如权利要求4所述的基板(1)，其特征在于，所述非贵金属接合搭接垫(2)至少部分延伸高出所述主表面(11)并且所述封盖层(3)仅覆盖所述非贵金属接合搭接垫(2)延伸高出所述主表面(11)的侧壁(14)。
9.如权利要求8所述的基板(1)，还包括材料层(4)，所述材料层至少部分覆盖所述非贵金属接合搭接垫(2)的所述顶侧(13)，所述材料层(4)包括金属互化物和填隙B，所述金属互化物包含非贵金属接合搭接垫(2)的金属与主焊料金属和Ni或Co的组合。
10.如权利要求8所述的基板(1)，还包括材料层(4)，所述材料层至少部分覆盖所述非贵金属接合搭接垫(2)上没有被所述封盖层(3)覆盖的部分，所述材料层(4)包括金属互化物和填隙B，所述金属互化物包含非贵金属接合搭接垫(2)的金属与主焊料金属和Ni或Co的组合。
11.如权利要求10所述的基板(1)，其特征在于，所述主焊料金属选自：Sn,Zn,Bi,Pb或In。
12.一种制造如权利要求1所述的基板的方法，所述方法包括：
-提供基板，所述基板在主表面上包括至少一个非贵金属接合搭接垫(2)，
-清洁所述基板(1)的所述主表面(11)，和
-将封盖层沉积到所述金属接合搭接垫经清洁的表面上，从而至少部分覆盖所述非贵金属接合搭接垫，
其特征在于，
-所述封盖层(3)包括合金，所述合金是NiB或CoB并且含有原子浓度百分率为10-50％的硼。
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