CN107530836B - 用于半导体管芯附接应用的具有高金属加载量的烧结膏剂 - Google Patents

用于半导体管芯附接应用的具有高金属加载量的烧结膏剂 Download PDF

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CN107530836B
CN107530836B CN201680023639.9A CN201680023639A CN107530836B CN 107530836 B CN107530836 B CN 107530836B CN 201680023639 A CN201680023639 A CN 201680023639A CN 107530836 B CN107530836 B CN 107530836B
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metal
composition
temperature
particles
alloy
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CN107530836A (zh
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C·施尔勒
E·巴拜尔
M·马修斯
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Ormet Circuits Inc
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Ormet Circuits Inc
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    • B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
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Abstract

一种半导体管芯附接组合物，其在热反应后具有大于60％的金属体积，该组合物具有：(a)80‑99重量％的金属颗粒混合物，该混合物包含30‑70重量％的无铅、低熔点(LMP)颗粒组合物，其包含至少一种LMP金属Y，该金属Y在低于温度T1时熔化，和25‑70重量％的高熔点(HMP)颗粒组合物，该高熔点颗粒组合物包含至少一种金属元素M，该金属元素M在处理温度T1下与所述至少一种LMP金属Y是反应性的，其中M的重量％与Y的重量％之比为至少1.0；(b)0‑30重量％的金属粉末添加剂A；以及(c)助焊载体，所述助焊载体具有挥发性部分和不超过50重量％的非挥发性部分。

Description

用于半导体管芯附接应用的具有高金属加载量的烧结膏剂
发明领域
本发明涉及金属组合物、其制备方法及其用途。更具体地，本发明涉及金属组合物、其制备方法以及其用于将半导体管芯(die)附接到封装元件的用途。
发明背景
在电子器件的生产中，将半导体管芯组装到基底上以产生用于将管芯信号输入和输出功能互连到将与之通信的其它器件的平台。典型地，利用设置在管芯的非功能侧与基底之间的专门设计的焊料和/或聚合物粘合剂来实施该组装。
在半导体管芯的某些子集(通常用于电源管理或照明应用)中，附接至基底的管芯侧面被金属化以便促进工作中的半导体管芯和基底之间的良好热传递，并且在一些情形中，也有利于电互连。为功率应用制造的硅基半导体管芯通常以这种方式进行金属化，以便实现与管芯背面的电连接和热连接两者。当器件工作温度升高时，以类似方式制备其它材料(如碳化硅和氮化镓)以便改善高温环境下的器件性能。
对于其中从管芯散发的热量相对较低的应用，填充金属颗粒的聚合物粘合剂是用于将半导体管芯粘附到封装元件的最常见类型的材料。在这些粘合剂体系中，热传导以及(如果需要时的)电传导基于金属填料的体积分数通过各种机制传播。研究(和工业实践)已表明，具有约30％的金属填料体积分数的导电粘合剂能够实现低的电阻率和高的热导率。然而，导电粘合剂在其电学可靠性性能方面具有固有的局限性，因此在半导体器件中它们替代软焊料的能力是有限的。由于热传导和电传导的效率直接取决于填料颗粒相对于聚合物粘合剂含量的比例，因此这些粘合剂的电导率存在上限，这是由能够纳入而不损害粘合剂的机械完整性的填料量的实际限制所引起的。
对于需要较高功耗的应用，使用焊料或银基烧结材料对于将半导体附接到封装元件是较为常见的。传统地，铅基焊料用于功率半导体的管芯附接，因为这些焊料很好地润湿金属化的管芯和封装元件，提供优异的电导率和热导率，并具有高的伸长率以减轻半导体管芯和封装元件之间的热膨胀系数(CTE)差异。在过去十年中，已经倡议用无铅焊料代替铅基焊料。对于特殊应用，使用金-锡、锡-锑、铟基或铋基合金，但是这些合金常常是昂贵的并且经常具有机械性能或电学性能的局限。对于更广泛的功率管芯附接应用，锡基焊料已被评估为无铅解决方案。通常，以膏剂或线基形式施用这些锡基焊料。在热处理期间，锡合金的各个颗粒熔化并彼此熔合并且金属化的表面形成整体接头。当各个颗粒瓦解并固结成单一熔融物质时，从该物质中排出挥发性助焊剂载体，从而导致空隙空间的大且集中的凹窝，助焊剂挥发物已被从所述空隙空间排出。由于在该部位缺乏热传导，或者因减小的电接触部面积导致降低的器件电性能，这些凹窝可能在半导体管芯上产生热点。尽管这些空隙凹窝是含铅和无铅焊料两者所特有的，但在无铅焊料中，随后的热漂移可能引起合金再次熔化，这可能导致空隙凹窝进一步合并成非常大的空位。此外，无铅的锡基合金不表现出铅基焊料的伸长率特性，因此无法有效地缓解半导体管芯和封装元件之间的CTE失配。
为满足功率半导体的需要所提出的一类材料被称为银烧结膏剂。银烧结膏剂包含与载剂结合的通常为纳米或微米尺寸的银颗粒。在热处理期间，纳米尺寸银颗粒的高表面能被用来在远低于银金属熔点的温度下将银颗粒烧结在一起。也可以在载剂组合物中使用有机金属添加剂以促进烧结性能。在热处理期间通常需要施加压力(并非半导体附接的典型制造协议)以实现足够结实和机械牢固的接头。虽然这类材料提供许多理想的特性，但这些昂贵的材料通常不能很好地粘结到因成本原因而日益普遍的许多封装元件表面上。
因此，该行业目前在寻找用于将金属化的半导体管芯附接到封装元件的替代类型材料。该新材料类型的期望属性是使用现有的沉积和处理设施；高的热导率(>20W/mK)；稳定的电阻，牢固的粘附力，通过多重热漂移的机械和电学可靠性，包括标准工业可靠性测试；接头中的空隙体积低以及空隙尺寸小；差式热膨胀系数(CTE)机械应力管理；和低成本。
发明概述
在本发明的一个方面，本发明涉及将金属化的半导体管芯附接到封装元件上，例如夹具、引线框、基底、中介层(interposer)和引线，以便实现牢固的电互连和热互连。本发明的组合物是新类型的半导体组装材料，其具有用于将高功率应用的半导体管芯互连所需的所有属性，并且弥补现有技术组合物的缺陷。
本发明的组合物利用两种或更多种类型的金属颗粒与助焊有机载体(vehicle)结合以产生膏剂。选择两种或更多种类型的金属颗粒以便在特定工艺温度下不可逆地反应从而形成连续的冶金互连网络，从金属化封装元件上的附着点，通过所设置组合物的本体，并终止于半导体管芯的金属化连接点。本发明的助焊载体用于以膏剂形式提供金属颗粒，促进金属颗粒之间的反应，并且在热处理期间大量挥发，从而导致具有等于或大于60％的互连金属体积分数的接头。处理后接头中的互连金属的高体积分数导致与焊料相当的高、稳定且可靠的电性能和热性能。最终接头中的互连金属的高体积分数还决定处理后接头的机械特性，从而克服了现有技术的金属填充聚合物组合物的机械降解问题。组分金属颗粒的成本和处理要求与作为当前工业标准的焊料材料相当。
在一个实施方案中，可将本发明的组合物描述为：
a)无铅金属颗粒的混合物，其包含：
i)包含金属元素Y的低熔点(LMP)颗粒组合物；和
ii)包含金属M的高熔点(HMP)颗粒组合物，该金属M在处理温度T1下与金属Y是反应性的，
b)助焊载体，其中所述助焊载体包含：
i)挥发性部分，和
ii)不超过50重量％的在T1下变为惰性的非挥发性部分。
附图简述
图1描绘了使用本发明组合物将一个半导体管芯连接到两个封装元件的示例性用途。
图2描绘了刚制备以及在T1下热处理的本发明组合物之间的转变。
发明详述
应当理解，前面的一般性描述和下面的详细描述都是说明性和解释性的，并不是对所要求保护的主题的限制。
本文使用的章节标题是出于组织目的，而不应被解释为限制所描述的主题。出于任何目的，通过引用将本申请中引用的所有文献或文献部分以其整体明确地并入本文，包括但不限于专利、专利申请、文章、书籍和论文。如果一份或多份并入的文献和类似材料中的术语定义与本申请中该术语的定义相矛盾，则以本申请为准。
如果未提供具体的定义，则与本文所述的材料科学、冶金学、冶金工程、电子和化学有关的命名以及实验室程序和技术是本领域公知的。标准化学符号与这些符号所表示的全名可互换地使用。因此，例如，术语“锡”和“Sn”被理解为具有相同的含义。标准技术可用于冶金加工、焊接、化学合成、化学分析和配方。
定义
在本申请中，单数的使用包括复数，单词“一(a)”或“一(an)”表示“至少一”，并且“或”的使用表示“和/或”，除非另有具体说明。此外，术语“包括(including)”以及其它形式例如“包括(includes)”和“包括(included)”的使用不是限制性的。另外，诸如“元件”或“部件”的术语不但包括含一个单元的元件或部件而且包括含多于一个单元的元件或部件，除非另有具体说明。如本文中所使用的，连词“和”意图是包括性的而连词“或”并不意图是排他性的，除非另有说明。例如，短语“或者，作为替代”意图是排他性的。如本文中所使用的，术语“和/或”是指包括使用单一元件的前述要素的任何组合。
此外，术语“包括(including)”以及其它形式例如“包括(includes)”和“包括(included)”的使用被理解为“包含”并且不是限制性的。应理解，如说明书和权利要求书中所使用的，任何词语的单数形式也可以指复数，这取决于使用其的上下文。
本文中所使用的“约”或“大约”是指：被称为“约”或“大约”的数字包含所述数字加上或减去所述数字的1-10％。例如，根据情况，约50度可表示45-55度或仅49-51度。
无论何时在本文中出现时，数值范围例如“45-55”是指在给定范围内的每个整数；例如，“45-55％”意指该百分比可为45％、46％等，直到且包括55％。当本文中所述范围包括小数值时，例如“1.2％-10.5％”，该范围是指在给定范围内指示的最小增量的每个小数值；例如“1.2％-10.5％”意指该百分数可为1.2％、1.3％、1.4％、1.5％等直到并且包括10.5％；而“1.20％至10.50％”意指该百分数可为1.20％、1.21％、1.22％、1.23％等直到并且包括10.50％。
如本文所用，术语“基本上”是指大的程度或等级。例如，“基本上所有”典型指至少约90％，通常至少约95％，经常至少99％，且更经常至少约99.9％。
术语“合金”是指含有两种或更多种金属以及任选地另外的非金属的混合物，其中当熔融时所述合金的元素熔合在一起或溶入彼此。本文关于合金组合物所用的符号使用其IUPAC符号列出两种或更多种元素，以斜杠(“/”)隔开。当给出时，通过对应于该元素在合金中的重量百分比的下标来表示该元素在合金中的比例，例如，Sn/Bi表示锡(Sn)和铋(Bi)的合金，其可以是这两种元素的任意比例。Sn(60)/Bi(40)表示包含60重量％锡和40重量％铋的锡与铋的特定合金。当为合金中元素的重量百分比给出范围时，所述范围表示该元素可以按所指示范围内的任何量存在。例如，Sn(70-90)/Bi(10-30)是指含有70重量％至90重量％锡以及10重量％至30重量％铋的合金。因此，“Sn(70-90)/Bi(10-30)”范围包含的合金包括但不限于：Sn(70)/Bi(30)，Sn(71)/Bi(29)，Sn(72)/Bi(28)，Sn(73)/Bi(27)，Sn(74)/Bi(26)，Sn(75)/Bi(25)，Sn(76)/Bi(24)，Sn(77)/Bi(23)，Sn(78)/Bi(22)，Sn(79)/Bi(21)，Sn(80)/Bi(20)，Sn(81)/Bi(19)，Sn(82)/Bi(18)，Sn(83)/Bi(17)，Sn(84)/Bi(16)，Sn(85)/Bi(15)，Sn(86)/Bi(14)，Sn(87)/Bi(13)，Sn(88)/Bi(12)，Sn(89)/Bi(11)，和Sn(90)/Bi(10)。此外，Sn(70-90)/Bi(10-30)表示其中元素Sn和Bi的具体比例可从Sn(70)/Bi(30)到Sn(90)/Bi(10)变化的合金，包括从70重量％上至90重量％变化的Sn比例以及从30重量％下至10重量％反向变化的Bi比例。
术语“假合金”是指包含金属元素的混合物的微粒，其中当处于熔融形式时金属元素不溶入彼此。通过从非熔体的熔融状态使元素共凝固形成“假合金”颗粒，使得每个颗粒包含共凝固元素的混合物。
本文所用的“助焊剂”是指用于促进金属熔化且特别是去除和防止金属氧化物形成的物质，通常为酸或碱。
本文所用的术语“熔化温度”或“熔点”是指在大气压力下固体变成液体的温度(点)。
本文所用的术语“高熔化温度金属”、“高熔点金属”或“HMP金属”是指熔化温度等于或高于约400℃的金属。HMP金属包括Cu、Ag、Pd、Au、Al、Ni、Be、Rh、Co、Fe、Mo、W、Mn和Pt。典型地，本发明组合物中使用的HMP金属为Cu、Ag、Pd、Au、Al、Ni或Pt，并且最常见地HMP金属为Cu、Ni或Ag。
本文所用的术语“低熔化温度金属”、“低熔点金属”或“LMP金属”是指熔化温度低于约400℃的金属。示例性的LMP金属包括Sn、Bi、Zn、Ga、In、Te、Hg、Tl、Sb、Se、Po、Pb、Cd和Po，以这些金属的合金形式。典型地，用于本发明组合物中的LMP金属是以合金形式的Sn、Ga、In或Zn，且最常见地，所述LMP为合金形式的Sn。
术语“固相线”是指这样的温度：低于该温度时给定物质完全为固体(结晶态)。固相线对物质熔化开始、但不一定完全熔化的温度进行量化，即固相线不一定是熔点。由于该区别，固相线可与“液相线”形成对比，液相线指定晶体能够与熔融物质共存的最大温度。高于液相线温度时，材料在平衡时是均匀的并且为液体。低于液相线温度时，越来越多的晶体可以形成。在所有情况下，固相线和液相线温度不会对齐或重叠。如果在固相线温度和液相线温度之间存在间隙，则将其称为“凝固范围”或“糊状范围”，并且在所述间隙内，物质由固相和液相的混合物组成。
术语“共晶”是指这样的混合物或合金：其中多个组分部分的存在比例使得所述组分同时熔化，并且熔点尽可能低。因此，共晶合金或混合物在单一温度下凝固。在共晶混合物中，固相线和液相线温度相同，即，该混合物在一个温度即共晶点下完全熔化，
术语“非共晶”是指不具有共晶性质的混合物或合金。因此，当非共晶合金凝固时，其组分在不同温度下凝固，从而整个组合物表现出熔化范围。
术语“粉末”或“颗粒”或“微粒”是指离散形式的凝固金属组分，典型在1纳米至100微米的尺寸范围内。
术语“差示扫描量热法”(“DSC”)是指一种热分析方法，其中测量增加样品和参比物的温度所需的热量差异随温度的变化。DSC用于研究合金颗粒的熔化行为以及用金属和合金配制的TLPS膏剂的反应特征。
术语“烧结”是指其中金属粉末颗粒的相邻表面通过加热而结合的过程。“液相烧结”是指其中固体粉末颗粒与液相共存的烧结形式。随着金属扩散到彼此中并形成新的合金和/或金属间化合物类，发生混合物的致密化和均匀化。
在“瞬时液相烧结”或“TLPS”中，液相仅存在短的时段，由于金属的均匀化从而形成固体合金和/或金属间化合物类的混合物。液相在周围的固相中具有非常高的溶解度，因此快速扩散到固体中并最终凝固。扩散均匀化产生最终的组合物，而不需要将混合物加热到高于HMP金属的固相线温度。
本文所用的“熔化热”或“熔化焓”是指在不改变物质温度的情况下使物质从固态转变为液态所需的能量。该转变发生的温度即为熔点。因此，熔化热是“潜热”，因为在熔化期间不能作为温度改变而观察到热量的引入，并且在该过程期间温度保持不变。
“焊料”是用于将金属零件连接在一起并且熔点低于工件熔点的可熔金属合金。焊料具有不随反复热/冷循环显著改变的特征熔化行为。焊料可以包括共晶或非共晶合金，但共晶合金优选用于连接应用，因为接头快速凝固。TLPS不同于焊料，因为在TLPS组合物中存在HMP金属，其与TLPS低熔化温度合金中的反应性LMP金属相互作用从而形成具有特定化学计量比例以及比原始TLPS组合物高得多的熔化温度的晶态金属间化合物。因此，TLPS组合物通常不会在初始加处理温度下再次熔化。虽然金属间化合物可以在焊料内以及在焊料和连接表面(例如铜垫)中的元素之间形成，但是它们仅占焊接接头的小比例(＜5％)。因此，可在与初始施用基本上相同的条件下再次熔化所施用的焊料。
本文所用的“回流”或“回流焊接”是指用于将一个或几个电子部件附接到例如接触垫或其它基底的工艺，其中使所附接的部件和基底/接触垫的组装件经受足以使焊料熔化、流动并凝固的受控热，从而在零件和焊料之间形成永久的电子机械结合。
术语“延展性”或“延性”是指固体材料在拉应力下变形的能力；这典型地通过材料被伸展成例如线材的能力来表征。固体材料的类似但可区分的性质是“展延性(malleability)”，其是材料在压应力下变形的能力，并且通过用锤击或轧制而形成薄片的能力来表征。
“热膨胀系数”或“CTE”是描述物质的热力学性质的术语。CTE将温度变化与材料的线性尺寸变化相关联。
本文关于TLPS组合物所用的术语“处理温度”或“T1”是两种反应性金属(例如Cu和Sn)形成金属间化合物类的温度。
术语“金属间化合物”或“金属间化合物类”是指一种固体材料，其由一定比例的两种或更多种金属原子组成，该固体材料具有与其组分金属不同的明确结构。
本发明的组合物
本发明组合物是将半导体管芯附接到封装元件的软焊料和填充金属的聚合物的替代物。本发明组合物的高体积金属加载量和低孔隙率在半导体和金属封装元件之间提供优异的机械性能，电和热互连性能。
在本发明中，使金属颗粒与无铅金属合金颗粒在助焊载体中混合。无铅金属合金颗粒内的至少一种元素与金属颗粒中的金属是反应性的。当温度升高到无铅金属合金颗粒的熔点时，无铅金属合金颗粒变熔化。来自无铅金属合金颗粒和接受性金属颗粒的反应性元素的扩散和反应继续直至反应物完全耗尽，在处理温度下不再存在熔融相，或者通过冷却混合物使反应猝灭。在冷却之后，在反应后的材料中金属的体积分数超过总体积的60％，和/或在反应后的材料中空隙的总体积分数小于10％。反应后的本发明组合物的随后温度漂移(甚至超出初始熔体温度)不会再现混合物的初始熔体特征。
本发明组合物克服了如下问题：焊料管芯附接材料中的大空隙和再熔化，以及具有相对较低金属加载百分比的被动加载的导电粘合剂组合物的不良热性能，同时还提供了与普通制造方案的顺应性以及与通常表面光洁度的兼容性。在本发明组合物中，将金属颗粒与无铅焊料膏组合物共混并用助焊载体溶剂稀释使得热处理后的金属净含量超过60体积％。可以按一定膏剂稠度(consistency)制备本发明的组合物，以便有利于通过常用工业方法进行施用，例如分配和丝网印刷。一旦施用糊剂并且以期望的构造组装半导体和封装元件，使组装件经受在受控热上升(ramp)和环境下的热漂移(excursion)。在该热处理期间，助焊载体中的挥发性部分缓慢蒸发，无铅金属合金颗粒熔化，熔融合金中的LMP金属Y扩散进入金属元素M的相邻表面并反应从而形成高熔点合金。剩余的助焊载体，以及填充颗粒之间的间隙的助焊剂化学成分，热固化并且变为化学惰性。所得到的组合物含有至少约60体积％的冶金互连的金属。
本发明组合物优于传统的填充颗粒的粘合剂，因为机械强度以及热性能和电性能来自于通过使无铅合金颗粒中的LMP金属(例如锡)中相互扩散进入半导体管芯的可焊接表面、封装元件和金属颗粒中从而形成高体积加载量的冶金互连路径。在常规的填充颗粒的粘合剂中，通过维持聚合物粘合剂的机械完整性的需要来限制所述体积金属加载量。
本发明组合物优于常规的含铅焊料和无铅焊料，因为本发明组合物是无铅的并且当在部件组装到模块或印刷电路板期间暴露于随后的焊料回流温度曲线(profile)时将不会再次熔化。
本发明组合物不同于现有技术的组合物，因为已对本发明组合物进行专门设计以满足功率半导体管芯附接的独特挑战，例如非常低的空隙体积和高体积的密集互连金属以实现高的热性能和电性能。首先，低的空隙百分比取决于在所限定的热处理方案期间助焊剂载体的挥发性部分的受控挥发。此外，通过使助焊载体的非挥发性部分最小化以及优化无铅金属合金颗粒与金属颗粒之间的比例来实现高体积分数的互连金属。最后，已经对本发明组合物中的金属粉末的颗粒尺进行选择以便提供改进的结合控制以及用于管芯附接应用的施用简易性。
在最简单的情况下，本发明的半导体管芯附接组合物是金属粉末和助焊载体的组合物，该组合物一旦反应则形成包含至少60体积％的金属(合金+金属粉末)部分和/或小于10体积％的空隙部分的冶金互连网络。该组合物包含：
a.80-99重量百分比(重量％)的金属颗粒混合物，该混合物包含：
i.30-70重量％的无铅、低熔点(LMP)颗粒组合物，其包含至少一种LMP金属Y；和
ii.25-70重量％的高熔点(HMP)颗粒组合物，其包含至少一种金属元素M，该金属元素M在处理温度T1下与所述至少一种LMP金属Y是反应性的，
其中，M的重量％与Y的重量％之比为至少1.0，
b.0-30重量％的金属粉末添加剂A，以及
c.助焊载体，其中所述助焊载体包含：
i.挥发性部分，和
ii.不超过50重量％的在T1下变为惰性的非挥发性部分。
在本发明的实施中，无铅金属合金颗粒、金属粉末和助焊载体可混合在一起形成可印刷或可分配的膏剂(paste)。典型地，无铅金属合金和金属颗粒的混合物的存在量将为所述组合物的至少约80重量％，或至少约85重量％，并且为所述组合物的至多约90重量％，或至多约95重量％，或至多约99重量％。典型地，无铅金属合金粉末的存在量将是所述混合物的至少约20重量％，或至少约30重量％，并且为所述混合物的至多约50重量％，或至多约60重量％，或至多约70重量％。通常，金属粉末的存在量将为所述混合物的至少约30重量％，或至少约40重量％，并且为所述混合物的至多约70重量％，或至多约80重量％。典型地，助焊载体的存在量将是所述组合物的至多约20重量％，或至多约10重量％，或至多约5重量％，其中不超过约50重量％，或约25重量％，或约10重量％，或约5重量％的助焊载体是非挥发性的。典型地，组合物中M的重量百分比与Y的重量百分比的比例为至少约1.0，或至少约1.3，或至少约1.5。
本发明组合物可有利地用于将半导体芯片的顶面和/或背面连接到半导体封装元件，例如夹具、引线框或其它基底。本发明组合物最有利地用于形成组装件：其中半导体芯片的顶面和/或背面和封装元件都用可焊接表面金属化以便促进半导体芯片与封装元件之间的热传递和/或电连接。这种构造使得本发明组合物能够形成连续的冶金互连路径：从半导体管芯上的金属化层，通过所述接头的本体，并且直到封装元件上的金属化层(metallization)。
本发明组合物可以是基于膏剂的或可转化成膜。本发明组合物可以被网版印刷或丝网印刷、分配、喷射、拾放、层叠等，以便在半导体芯片表面、封装元件表面、或者临时承载物(半导体芯片和封装元件然后可附接于该临时承载物)上形成图案化的沉积物。存在于助焊载体组合物中的挥发物要么在b-阶段过程中要么在温度上升到峰值温度T1的过程中释放。T1等于或大于无铅金属合金颗粒的熔化温度。在焊料回流中，通常选择峰值回流温度为超过无铅金属合金颗粒的熔化温度5-50℃，以确保所有颗粒变为熔融和流体。该峰值温度也适合于本发明组合物，但是可需要较长的总工艺周期时间以便实现挥发性组分的释放以实现期望的低空隙体积百分比，并且形成相互扩散的冶金结构。
在本发明组合物的热处理漂移期间，无铅金属合金颗粒中的LMP金属(例如锡)与组合物中的剩余金属颗粒发生相互扩散，导致不可逆地形成具有显著超过回流处理温度的熔化温度的新合金组合物。正是该特征使得本发明组合物能够用于将半导体管芯附接到封装的部件中，在将封装的部件组装到电路板时无需在随后的回流操作期间再次熔化。
无铅金属合金颗粒也可以含有与金属颗粒呈非反应性的元素。可与反应性元素合金化的典型元素可包括Bi、Ag、Cu、Sb、Au或其组合。通常，掺入这些附加的非反应性元素以实现特定的处理温度，以改善对优选金属表面(例如铜)的湿润，或者操纵经热处理的组合物的机械性能。特定的合金化元素可以在一个方面是有利的，例如提供低的处理温度，但是在另一方面(例如湿润和粘附到特定表面光洁度)是有害的。因此，特定的合金化元素是特定于(specific to)应用的具体要求。
在半导体管芯和封装元件之间的最终接头中存在空隙通常对热性能是有害的，并且可能产生机械失效的萌生点。可以用类似于通常用于焊料的热曲线的方式或者以与导电粘合剂一致的方式处理本发明组合物。应选择所使用的热曲线以便将反应组合物中的空隙总体积限制到小于约10％或小于约5％。应选择从该曲线的峰值温度到室温的冷却速度以防止因热冲击对半导体芯片的损伤，且所述冷却速率例如小于约6℃/秒，或在约2.17℃/分钟和约3.25℃/分钟之间。应理解，最佳冷却速率可能取决于所使用的处理类型(例如，在粘合剂型处理中显著慢于回流型处理)和具体的半导体管芯和封装形式的因素。
TLPS组合物的热固性(thermosetting)性能
本发明的组合物是基于以下观察结果：可在温度T1下处理TLPS组合物以连接电子部件并且所产生的处理后连接在随后加热到温度T1以及甚至更高的温度时将是稳定的。换而言之，一旦经受冶金处理，当加热超过处理温度时TLPS组合物不会熔化。因此，该TLPS组合物的行为类似于“热固性材料”，而不是“热塑性塑料”。
技术人员将认识到，在施加热量时“热固性材料”不可逆地“固化”从而变得不可溶，而“热塑性材料”在被加热时熔化，当充分冷却时凝固，并且可反复地再次熔化和再次凝固。尽管该术语通常用于描述聚合物粘合剂，但是在本文中使用其描述用于连接例如电子部件和其它金属元件的冶金组合物。
常规的金属焊料可被表征为“热塑性”。焊料熔化以将金属零件接合在一起并在冷却时凝固从而将这些零件保持在适当位置；然后，当随后再次加热时，焊料再次熔化。相比之下，TLPS组合物的行为类似热固性材料。当被加热时，TLPS组合物充分熔化从而将金属零件连接在一起，并在冷却时凝固从而将这些零件保持在适当位置。然而，在熔融过程期间，TLPS组合物经历不可逆的冶金变化，可将其视为“固化”，结果是“固化”或经处理的TLPS组合物在再次加热时将不会熔化。
在本发明的某些实施方案中，将含有低熔点(LMP)无铅金属合金的常规焊料膏与反应性金属颗粒结合，它们的比例可将焊料转化为“热固性”形式，在典型的焊料回流周期过程中其不可逆地“固化”。这种“热固性”行为导致在初始回流温度下不会再次熔化的接头，因此该接头适合于在相同回流温度下的二次组装周期以及适用于高工作温度的应用。
在常规的焊料回流中，回流温度通常选择为超过焊料膏熔化温度5-50℃，以确保所有的颗粒变为熔化和流体。当使用本发明组合物代替用于附接电子部件的焊料膏时，可遵循标准的焊料回流实践。
在本发明的实施中，选择高熔点金属M和至少一种LMP金属Y，使得瞬时液相烧结反应的产物将具有适于预期应用的属性的最佳组合。对于M的选择可以考虑的关键属性包括诸如以下的特征：热稳定电阻、延展性、高电导率和热导率、类似于周围材料的热膨胀系数，以及在特定情况下可能为期望的其它特征。
本发明组合物在回流焊接条件下经历热固化反应，从而形成晶态金属间化合物和合金产物(即在TLPS反应期间形成的新合金)的混合物，它们全部具有比初始无铅金属合金颗粒熔化温度显著更高的熔化温度，并且大大超过回流处理温度。在TLPS处理期间形成的合金产物与LMP和HMP金属颗粒的初始混合物相比具有显著不同的组成。该反应是不可逆的，并且经处理的组合物在随后的高温暴露期间不会显著熔化。正是该特征使得本发明组合物能够用于电子部件的标准回流附接，而不会在随后的回流操作期间再次熔化。因此，本发明组合物使得能够进行焊接操作以及在标准工业焊料回流条件下制造高工作温度的电子组装件，而无需使用铅、昂贵的元素例如金或外来合金(exotic alloy)。
在使用本发明组合物的焊料回流期间形成的晶态金属间化合物包含固定元素比例的单胞和限定晶粒尺寸的多重性结构。晶态金属间化合物是大强度但却脆的材料。当在标准焊料膏和部件附接垫之间的界面处形成金属间化合物时，大的晶粒通常随所述垫与本体焊料的层状界面一起生长。这些层状界面易于裂纹形成和扩展。然而利用本发明的组合物，反应性金属粉末成核为大量的不同取向的小且无序的晶粒。这些大量晶粒的生长受到每个颗粒中的反应性金属体积的限制。每个晶粒的随机取向防止所述小晶粒合并成少数大晶粒。这些大量的小且无序晶粒促进坚固接头的形成，该接头对裂纹扩展不如沿层状界面的少数大晶粒那么敏感。
典型地，在无铅金属合金颗粒的熔化温度下本发明组合物的熔化热在起始焊料回流过程期间减小至少70％。在起始处理期间，TLPS组合物在无铅金属合金颗粒的熔化温度下表现出大的熔化热峰值。在处理之后，再次加热到无铅金属合金的熔化温度时的熔化热也显著减小，即使当关于总组成中的比例进行归一化。
将一克物质从固态改变到液态而不改变其温度所需的能量称为熔化热。任何材料的熔化热都是该材料所特有的。在TLPS组合物内的LMP金属的融化热表达将取决于LMP金属在总组合物中的比例。由于M与Y反应形成金属间化合物类，可以通过将未处理组合物的样品与已在T1下处理过的组合物样品进行比较来确定在处理之后任何给定TLPS组合物中的LMP金属相的消耗。因为未处理组合物中的LMP金属的熔化热可能被与Y和M的TLPS反应相关的剧烈能量释放所掩盖，因此通常有用的方式是：使用纯LMP金属的熔化热，并然后根据LMP金属在组合物中的重量百分比将该值归一化从而获得未处理TLPS组合物的值。
高熔点金属
HMP金属(M)包括但不限于Cu，Ag，Pd，Au，Al，Ni，Be，Rh，Co，Fe，Mo，W，Mn和Pt。典型地，本发明组合物中使用的HMP金属是Cu，Ag，Pd，Au，Al，Ni或Pt，且最常见地HMP金属是Cu，Ni或Ag。包含M的HMP颗粒可以基本上是单质M，可以是与其它元素合金化的M，可以是涂覆到非金属核心颗粒或其它核心颗粒上的M，或者可以是本身用另一元素、无机涂层或有机涂层涂覆的M。考虑使用多种HMP金属以便获得具有最佳特性的TLPS反应产物。例如，在一些应用中，处理过的组合物的机械强度不如电导率重要，或者热导率可以比延展性更重要。由于通常必须优化一种性质而牺牲另一性质，因此可以根据本领域公知的元素性质来选择各个成分以便在预期应用中提供最佳性能。特别考虑银、金、钯、镍和铝用于本发明的组合物和方法，单独地或以各种组合，包括与铜的组合。
在本发明中，Cu是(M)的优选元素，然而考虑其它金属作为应用的保证。还考虑使用与铜组合的另外高熔点金属，以便获得具有最佳特性例如低CTE或复合模量的无铅焊料的金属性反应产物。Ag、Au、Pd、Ni、Al、Fe、Mn、Mo和W也被特别考虑用作原生的或合金化的金属元素。
低熔点金属
理想地，为了替代电子工业使用的现有无铅焊料回流处理，本发明的TLPS组合物中使用的LMP金属是通常用于制造无铅焊膏的金属。示例性的LMP焊料膏合金(Y/X)包括但不限于Sn/Ag/Cu、Sn/Cu、Sn/Ag、Sn/Sb、Sn/In、Sn/Bi、Sn/Bi/Ag。虽然使用可商购合金是有利的，但可以用任何合适的合金来实施本发明。组分的确切比例可以变化，并且本发明考虑定制合金。在无铅金属合金颗粒的表示“Y/X”中，“X”表示与Y形成合金的至少一种金属。在本发明的一些实施方案中，X表示一种、两种、三种或更多种合金化金属。例如，本文中Y/X来表示Y的各种合金，其中Y为锡，以及X为单一金属，例如铜(Sn/Cu)、银(Sn Ag)、锑(Sn/Sb)、铟(Sn/In)和铋(Sn/Bi)。Y/X也用于表示下述各种合金：Y是锡且X表示两种金属，例如银和铜(Sn/Ag/Cu，例如SAC)，以及银和铋(Sn/Bi/Ag)。
LMP无铅金属合金中的示例反应性元素(Y)包括以下金属：Sn、Zn、Ga、In，单独地或者以与(X)的合金形式。典型地，本发明组合物中的Y是Sn或In，并且最经常地Y是Sn，为合金形式Y/X。在本发明的某些实施方案中，反应性金属Y是以低熔化温度合金Y/X形式存在的Sn，并且反应性HMP金属M是Cu、Ni或Ag。在本发明的一个实施方案中，Y/X是SAC(Sn/Ag/Cu)且M是Cu。
金属添加剂
本发明的方面是基于如下观察结果：包括金属添加剂能够改善处理过的TLPS组合物的性能，例如延展性。因此，通过将添加剂单质或合金粉末与上述主要金属M和Y或者合金粉末Y/X组分混合，将有益的金属添加剂(A)掺入TLPS冶金成分(metallurgy)中。这样的金属添加剂A参与到本发明的冶金成分中，要么作为固有反应性的组分要么作为通过用反应性金属元素涂覆、合金化或假合金化而具有反应性的组分。添加剂金属包括Cu、Ag、In、Pd、Au、Ni、Ce和Pt。如果用可与M或Y反应的金属进行合金化、假合金化或涂覆，那么其它金属如Be、Rh、Co、Fe、Mo、W和Mn也被考虑作为添加剂。
添加剂金属颗粒A的主要目的是在处理本发明的TLPS组合物时通过M与Y的反应形成的晶态金属间反应产物的基质内提供延性相。为了有效提高整体组合物的延展性，添加剂颗粒A必须冶金结合到基质中。如果A未结合到基质中，那么形成和扩展穿过脆性晶态相(例如金属间化合物)的裂纹将仅仅绕过延性添加剂颗粒A，而不是收获更加延性相的益处。然而，当添加剂颗粒A结合到基质时，由添加剂延性相赋予的增加延展性缓解裂纹扩展并允许接头承受增加的机械应变。
在本发明的某些实施方案中，在回流之后本发明组合物的部分再熔化不是有害的，例如当在二次回流操作中在TLPS接头上几乎没有机械载荷时。在这样的应用中，可以掺入过量的元素Y或合金Y/X以提供延性相。延展性也可以由与LMP合金Y/X中的Y合金化的元素赋予，从而当与M的反应耗尽Y时，使得延性相X可用。
当期望掺入延性相而不是过量的元素Y或合金Y/X时，存在至少两种掺入方式。第一种方法是以双峰颗粒尺寸分布(即含有HMP金属的小颗粒和大颗粒)掺入一种或多种HMP金属。HMP金属的较小颗粒用作与Y反应的HMP金属M TLPS试剂，而HMP金属的较大颗粒太大以致不能有效转变为金属间化合物类。因此，充当金属添加剂A的较大颗粒尺寸的HMP金属仅在颗粒表面上反应，而本体保持为未反应的延性金属。两种尺寸的HMP金属颗粒可以是相同或不同的HMP金属。
用于产生延性相的第二种方法是向本发明组合物中掺入与Y或M不具有反应性但是用金属添加剂A颗粒形式的反应性金属进行涂覆、合金化或假合金化的延性材料。在这种替代方案中，被涂覆、合金化或假合金化的反应性金属在冶金学上反应进入基质，留下延性材料不变从而形成延性相。
掺入添加剂A的前述方法也可用于控制所处理组合物的其它特性，例如热膨胀系数等。
颗粒尺寸、形状和比例
将高熔点金属M、金属Y或合金Y/X以及任选的金属添加剂A以颗粒(例如粉末)形式引入组合物中。所述颗粒可以是球形、不规则、薄片、海绵状、棒状和本领域技术人员已知的其它形式。HMP金属M的颗粒可以基本为单质，可以与其它元素合金化，可以作为涂层沉积到非金属或其它的核心颗粒上，或者其本身可以涂覆有另一种元素、无机涂层或有机涂层。类似地，LMP金属Y或包含Y/X的合金可以是仅由金属元素X与反应性LMP金属元素Y组成的二元合金，或者可以与其它成分合金化，可以沉积到非金属或其它的核心颗粒上作为涂层，或者其本身可以涂覆有另一种元素、无机涂层或有机涂层。
本发明组合物的关键特征是：颗粒尺寸分布被控制使得它们适合于在半导体管芯的平坦表面与接合表面之间产生薄且一致的粘结线。HMP金属M和LMP金属Y或合金Y/X的颗粒(例如粉末)典型具有约0.1μm至约100μm的名义直径。更常见的，金属粉末具有1μm至50μm之间的名义尺寸。
在一些实施方案中，在TLPS组合物中存在两种或更多种尺寸的颗粒，包括多种颗粒尺寸和颗粒混合物，其包括贯穿以下范围的颗粒：约1nm至约100μm，约10nm至约100μm，约100nm至约75μm，约1μm至约75μm，以及约1μm至约50μm。在一些情况下，通常通过努力筛分实现的颗粒尺寸分布的严格控制可用于使本发明的TLPS组合物适合于沉积技术，例如分配、喷墨等。典型地，HMP金属M、LMP金属Y或合金Y/X以及金属添加剂A的平均颗粒尺寸为1-50微米；最常见的其在5-20微米的范围内。
制造高温焊料/TLPS组合物的方法
本发明还提供了通过如下方式制备本文所述的TLPS组合物的方法：提供微粒形式的至少一种HMP金属M；微粒形式的至少一种LMP金属合金Y/X；任选地，微粒形式的金属添加剂A；和助焊载体；并以所公开的比例(基于组合物的总重量)将颗粒和助焊载体结合。
本发明还提供了制备本文公开的TLPS组合物的方法，该方法包括以下步骤：
1.提供微粒形式的至少一种HMP金属M，微粒形式的至少一种LMP金属Y和/或合金Y/X，助焊载体，和微粒形式的一种或多种金属添加剂A；和
2.以基于组合物总重量的所述比例将颗粒与助焊载体结合。
考虑用于本发明组合物的合金通常是可商购的。
颗粒涂层
涂层可以分别存在于第一颗粒和第二颗粒(分别包含M和Y)中的任一种或两种上，和/或存在于金属粉末添加剂A上。考虑使用的涂层包括金属、无机涂层、有机涂层和有机金属涂层。可以使用以涂层来制备颗粒，例如，以将另外的金属元素引入本发明的TLPS组合物中，以便改变处理过的金属基质的性质，保护颗粒免于氧化，防止金属或金属氧化物与有机成分的过早反应，促进颗粒在基质中的分散，保持颗粒处于悬浮，赋予组合物润滑性，防止颗粒附聚等。涂层存在和类型的具体选择取决于为TLPS组合物所考虑的应用，沉积方法和助焊载体的化学组成—所有这些都在本领域技术人员的知识范围内。金属(例如锡和银)，含磷结构部分如自组装的膦酸酯单层，饱和脂肪酸以及不饱和脂肪酸，无机金属盐和有机金属盐，金属醇盐，三唑和聚苯胺都被具体考虑作为根据本发明的有用涂层的组分。
助焊载体
本发明组合物的助焊载体充当金属颗粒的载剂(carrier)，用于将混合物保持在一起以便于施用并且保持各个颗粒彼此靠近。助焊载体还用于使金属试剂可用于反应并且保护它们免受环境影响，如同溶剂在有机反应中那样。若干因素决定着对于有机反应的合适溶剂的选择(例如极性、质子或非质子、与水的混溶性等)。同样，出于合适的属性选择本发明组合物中的助焊载体。助焊载体的最关键属性是：其必须从金属试剂的表面除去金属氧化物以使所述试剂可用于反应。金属氧化物的去除被称为“助焊”(fluxing)，并且可以通过本领域技术人员已知的各种化学物类来实现金属氧化物的去除，包括有机酸和强碱。
为了实现有用的膏剂稠度同时还实现具有最大金属含量的接头，助焊载体包含一种或多种挥发性组分。所述挥发性组分可以是充当助焊剂的活性物类，或者可以是化学惰性材料例如溶剂。在本发明组合物的热处理期间，所述挥发性成分在受控的升温和峰值温度条件下逐渐蒸发，使得在热处理后的接头中产生极少的空隙空间。
助焊载体可包括允许在处理之前根据需要对TLPS组合物进行成型的热塑性聚合物材料，并且可以含有聚合物前体和/或其它化合物以及溶剂，它们在处理期间反应从而在金属网络内形成互置的沉积物。
本发明TLPS组合物的应用
由本发明的TLPS组合物形成的冶金网络适用于电连接、热连接和/或机械连接电子结构内的元件。本发明提供了用于连接各种电子零件的组合物，所述电子零件用于可能遇到高工作温度的应用，包括但不限于分步焊接、井下、石油钻井、电子控制、汽车引擎室、智能电网分布和航空航天应用。
可以使用本发明组合物的示例性应用包括将半导体管芯连接到封装元件，从而在堆叠管芯等之间形成连接。
本发明的组合物可以有利地用于将金属化的半导体管芯连接到引线、电路板、引线框、夹具、中介层、另外的管芯或其它基底。本发明组合物最有利地用于连接半导体管芯，这时如此连接的组装件将经受需要另一焊料回流的后续组装操作和/或这时该组装件将用于恶劣的操作环境中。
可以使用各种技术来施用上述组合物，包括但不限于：针头分配(needledispensing)、模版印刷(stenciling)、丝网印刷、喷墨、层压、挤出、浇铸、喷涂或其它方法，这些技术将是本领域的技术人员公知的，例如形成图案化沉积物然后可将电子部件附接于其的方法。一旦施用，则在烘箱中、在回流炉中、在热板上、在层压压机中或者通过通常用于处理焊料或填充金属的有机粘合剂的其它装置对所述组合物进行热处理。具体的热处理条件取决于应用以及金属体系和任何有机粘合剂成分的选择。
在沉积之后，使金属半导体管芯或封装元件与沉积的本发明组合物接触从而形成组装件。然后可在烘箱中、在回流炉中、在热压设备中、在热板上、在层压压机中、或通过任何其它可用装置(例如通常用于处理焊料或填充的有机粘合剂的装置)将本发明的组合物热处理至温度T1。本领域技术人员将知晓通常用于处理焊料或填充的有机粘合剂的另外方法，这些另外方法将适合于处理本文所述的TLPS组合物。具体的热处理条件取决于应用、预期用途、TLPS组合物和任何助焊有机载体成分。典型地，处理温度T1在100℃至300℃的范围内，更通常在150℃至280℃的范围内，并且最通常在200℃至280℃的范围内。
图1描绘了用本发明组合物将一个半导体管芯连接到两个封装元件的示例性用途。半导体管芯40在两个主表面上被金属化(30和50)以提供电和热的互连点。将本发明组合物20设置在金属性封装元件10与半导体管芯40上的金属化层30之间。还将本发明组合物20设置在半导体管芯40上的金属化层50与非金属性封装元件70上的金属化层60之间。在图1中，本发明组合物被描绘为其在热处理到T1之前那样；其中各个颗粒仍然分散在助焊载体中。
图2描绘了本发明组合物在刚制备时和在T1下热处理后之间的转变。在每个描绘图中，本发明组合物20被设置在金属封装元件10与半导体管芯40表面上的金属化层30之间。在T1下热处理之前，HMP金属80和LMP金属90的各个颗粒在助焊剂载体100中是明显的。在T1下热处理之后，各个颗粒经历了相互扩散从而形成冶金互连的结构：从金属封装元件10，通过本发明组合物的沉积物20以及到半导体管芯40表面上的金属化层30。
现在将参照并通过以下的说明性、非限制性实施例进一步描述本发明。尽管出于清楚和理解的目的通过说明和示例的方式对本发明进行了相当详细的描述，但是本领域普通技术人员根据本发明的教导将明白可对其进行某些改变和修改而不脱离所附权利要求书的精神或范围。
实施例
现在将参照本公开的更具体实施方案以及为这些实施方案提供支持的实验结果。然而，申请人指出，下面的公开仅仅是为了说明的目的而并不意图以任何方式限制所要求保护的主题的范围。
比较例A-D
通过使用双行星式混合器在真空下于容器中将表1中列出的组分混合来制备四种比较膏剂(A-D)。
表1
比较例A 比较例B 比较例C 比较例D
组分 Wt％ Wt％ Wt％ Wt％
酚/叔胺 2.2 2.37 2.31 4.24
C<sub>6-20</sub>脂肪酸/叔胺 0.73 0.79 0.77 0.71
硅消泡剂 0.15 0.16 0.14
环脂族环氧化物 2.83
环脂族环氧化物阳离子催化剂 0.07 0.08 0.08 0.07
环氧树脂/环氧丙烯酸稀释剂 2.93 3.95 3.08 2.12
丙烯酸树脂 2.93 3.16 2.46
铜 36 46.75 49 44.3
SnBi共晶合金 22.1
SAC合金 15 20 23.5
Sn/Bi非共晶合金 40 27 22
气相法二氧化硅 0.75
在表2中给出比较例A-D的特性。在热处理之前和之后绘出金属百分比，并且将不同金属和聚合物组分的密度差归一化以提供处理后的金属体积分数。
表2
Figure BDA0001442643940000231
表2示出低体积的金属加载导致差的电可靠性，这意味着在可靠性测试期间大于10％的Rdson变化。在这些实施例中可注意到，可靠性能差的组合物在热处理后具有低的金属体积百分比。表1中的例子的组合物具有10-11重量％的残留在烧结组合物中的助焊剂载体，这导致相对较低的处理后金属体积百分比。
实施例1-4
通过使用双行星式混合器在真空下于容器中将表3中列出的组分混合来制备四种本发明组合物。
表3
Figure BDA0001442643940000241
在表4中给出实施例1-4的特性。在热处理之前和之后描绘金属百分比，并且将不同金属和聚合物组分的密度差归一化以提供处理后的金属体积分数。
表4
Figure BDA0001442643940000251
由于表2中的比较例，采用了新的方法以确保烧结后金属体积百分比增加。通过显著减少助焊有机载体的量并用挥发性溶剂代替它以维持组合物的膏剂稠度，充分提高处理后金属的体积百分比以实现期望的性能。出乎预料地，组合物中的助焊剂比例可被减少到远低于焊料膏中通常使用的比例，而不会对金属元素之间的期望TLPS反应产生有害影响。助焊有机载体的这种减少还导致处理后的有机相被降为孤立凹窝而不是连续相。因此，处理后的组合物出于预料地受互连金属网络机械控制，而不是表现为复合材料，这不同于现有技术的填充金属的聚合物粘合剂。表4显示了在烧结后具有较高金属体积百分比的膏剂中的可靠性和电性能的结果。
本发明的具有高体积的金属加载量并且利用无铅金属颗粒的混合物的无铅膏剂在机械和电学可靠性测试中的性能与含铅焊膏至少一样好。如通过表4中的实施例可观察到：与银-环氧化物粘合剂以及导致成功的可靠性结果的现有技术TLPS组合物相比，本发明组合物实现了高水平的粘附性以及高的电导率和热导率的出乎预料的组合。

Claims (13)

1.半导体管芯附接组合物，其在热反应后具有大于60％的金属体积，该组合物包含：
a.80-99重量百分比(重量％)的金属颗粒混合物，该混合物包含：
i.30-55重量％的无铅、低熔点金属合金颗粒组合物，其包含至少一种低熔点金属Y，所述至少一种低熔点金属Y选自Sn、Zn、Ga、In及其组合；和
ii.25-50重量％的高熔点颗粒组合物，其包含至少一种金属元素M，所述至少一种金属元素M选自Cu、Ag、Pd、Au、Al、Ni、Be、Rh、Co、Fe、Mo、W、Mn、Pt及其组合，其中M在100℃至300℃范围内的处理温度T1下与所述至少一种低熔点金属Y是反应性的，
其中组合物中的M的重量％与Y的重量％之比为至少1.0，
iii.20-45重量％的金属粉末添加剂A，所述金属粉末添加剂A包含已被可与M或Y反应的金属合金化、假合金化或者涂覆的Be、Rh、Co、Fe、Mo、W或Mn，以及
b.助焊载体，其中所述助焊载体包含：
i.挥发性部分，所述挥发性部分选自非反应性溶剂，和
ii.不超过50重量％的非挥发性部分，该非挥发性部分在T1下变为惰性，该非挥发性部分选自羧酸、酚及其组合，
其中所述助焊载体的存在量是1-20重量％。
2.根据权利要求1所述的组合物，其中所述金属元素M在T1下与至少一种低熔点金属Y发生相互扩散，使得由这种相互扩散形成的产物具有超过T1的熔点。
3.根据权利要求1或2所述的组合物，其中所述低熔点金属合金颗粒组合物不含超过痕量可检测水平的铋。
4.根据权利要求1或2所述的组合物，其中所述至少一种金属元素M选自Cu、Ag、Pd、Au、Al、Ni、Pt及其组合。
5.根据权利要求1或2所述的组合物，其中所述至少一种低熔点金属Y选自Sn、In及其组合。
6.根据权利要求1或2所述的组合物，其中T1在150℃至280℃的范围内。
7.根据权利要求1或2所述的组合物，其中所述金属粉末添加剂A的最大颗粒尺寸为50微米。
8.包含根据权利要求1或2所述的组合物的结构，该结构被设置在半导体管芯和封装元件之间，所述半导体管芯在至少一个主表面上带有金属化层，所述封装元件在至少一个主表面上带有金属化层。
9.一种形成连续冶金互连路径的方法，其包括如下步骤：在处理温度T1下处理权利要求8所述结构从而实现从带有金属化层的管芯到带有金属化层的封装元件的连续冶金互连路径。
10.根据权利要求9所述的方法，其中处理温度T1在150℃和280℃之间。
11.根据权利要求9或10所述的方法，其中在处理温度T1下的持续时间为15至75分钟。
12.根据权利要求9或10所述的方法，其中达到处理温度T1的升温速率在2.67℃/分钟和4.4℃/分钟之间。
13.根据权利要求9或10所述的方法，其中从处理温度T1返回到室温的冷却速率在2.17℃/分钟和3.25℃/分钟之间。
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