CN109326530B - 将导体焊接到铝金属化物 - Google Patents

将导体焊接到铝金属化物 Download PDF

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Publication number
CN109326530B
CN109326530B CN201810856761.5A CN201810856761A CN109326530B CN 109326530 B CN109326530 B CN 109326530B CN 201810856761 A CN201810856761 A CN 201810856761A CN 109326530 B CN109326530 B CN 109326530B
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oxide layer
aluminum
replacement metal
halide
conductor
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CN109326530A (zh
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A·海因里希
李五湖
R·奥特伦巴
W·赖斯
E·里德尔
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Infineon Technologies AG
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Infineon Technologies AG
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Abstract

一种将导体焊接到铝金属化物的方法包括：用替代金属氧化物层或替代金属合金氧化物层替代所述铝金属化物上的铝氧化物层。然后，至少部分地还原所述替代金属氧化物层中的或所述替代金属合金氧化物层中的替代金属氧化物。使用焊料材料将所述导体焊接到所述铝金属化物。

Description

将导体焊接到铝金属化物
技术领域
本公开总体上涉及半导体器件制造中的焊接技术，特别涉及将导体焊接到铝金属化物的多个方面。
背景技术
焊接工艺广泛用于半导体器件制造中，以用于各种目的，包括芯片结合、丝/夹/带式结合、器件安装等。多种焊料材料、助焊剂和焊接技术可供使用。焊接方法和焊接物质可以对半导体器件的成本、产量、性能和可靠性产生很大的影响。
铝(Al)金属化物的焊接需要施加高反应性的化学物质(助焊剂)以去除Al金属化物上的高度稳定的Al2O3层。这种高反应性的化学物质与标准半导体制造工艺不相容。因此，目前在Al表面上的焊接限于半导体器件制造之外的应用。
发明内容
本公开的一个方面涉及一种将导体焊接到铝金属化物的方法。所述方法包括用替代金属氧化物层或替代金属合金氧化物层替代铝金属化物上的铝氧化物层。替代金属氧化物层或替代金属合金氧化物层中的替代金属氧化物至少部分地被还原。使用焊料材料将导体焊接到铝金属化物上。
本公开的另一个方面涉及一种将导体焊接到铝金属化物的方法。所述方法包括将助焊剂材料施加到铝金属化物上的铝氧化物层。将焊料材料沉积在铝金属化物之上，其中，焊料材料具有按重量百分比(％重量)计为x％重量≤Zn≤100％重量的化学组成，其中，x＝10、30、50、70、90、95或100。然后，将导体焊接到铝金属化物上。
本公开的另一个方面涉及一种将导体焊接到铝金属化物的方法。所述方法包括经由等离子体工艺将卤化物施加到铝金属化物上的铝氧化物层，以产生卤化铝氧化物层。将焊料材料沉积在卤化铝氧化物层之上。然后，将导体焊接到铝金属化物上。
本公开的另一个方面涉及一种导体与铝金属化物焊接在一起的装置。所述装置包括沉积在铝金属化物之上的替代金属层或替代金属合金层，其中，替代金属层或替代金属合金层的替代金属可以是Zn、Cr、Cu、Pb和Sn中的一种。所述装置还包括布置在替代金属层或替代金属合金层与导体之间的焊料层。
附图说明
包括附图以提供对多个方面的进一步理解，附图包括在说明书中并构成本说明书的一部分。附图示出了本公开的各方面，并且与说明书一起用于解释本公开的各方面的原理。其它方面和多个方面的许多预期优点将会更容易明白，这是因为通过参考以下详细描述它们会变得更好理解。附图的元件不一定相对于彼此成比例。相同的附图标记可以指代相应的类似部件。应当理解，除非另有特别说明，否则下面描述的实施例的各种示例的特征可以彼此组合。
图1A是示出了铝金属化物和铝金属化物上的铝氧化物层的一个示例的剖视图。
图1B是示出了图1A的铝氧化物层的示例性活化过程的剖视图。
图1C是示出了用替代金属氧化物层或替代金属合金氧化物层对图1A或图1B的铝氧化物层的示例性替代过程的剖视图。
图1D是示出了图1C的替代金属氧化物层或替代金属合金氧化物层的示例性还原的剖视图。
图1E是示出了在图1D的还原过程之后的铝金属化物的剖视图。
图1F是示出了将焊料沉积物示例性地施加在图1E的铝金属化物之上的剖视图。
图1G是示出了将导体示例性地放置在图1F的焊料沉积物上的剖视图。
图1H是示出了根据图1G的放置在焊料沉积物上的导体的示例性焊接和冷却的剖视图。
图1I是示出了通过如例如图1A至1H中所示的示例性过程焊接到铝金属化物的导体的一个示例的剖视图。
图2是示出了在N2中5％H2(合成气体)的还原气体中的金属氧化物Al2O3、Cr2O3和ZnO以及在N2中CH2O2的还原气体中的金属氧化物Al2O3的计算出的以H2O的Pa为单位的平衡压力p与以K为单位的温度T的关系图。
图3A是示出了将焊料沉积物示例性地施加在图1C的铝金属化物之上的剖视图。
图3B是示出了将导体示例性地放置在图3A的焊料沉积物上的剖视图。
图3C是示出了根据图3B的放置在焊料沉积物上的导体的示例性焊接和冷却的剖视图。
图3D是示出了通过如例如图1A至1C中所示的示例性过程，接着通过如例如图3A至3C中所示的示例性过程焊接到铝金属化物的导体的一个示例的剖视图。
图4A是示出了将焊膏示例性地施加在图1A的铝金属化物之上的剖视图。
图4B是示出了将导体示例性地放置在图4A的焊膏上的剖视图。
图4C是示出了根据图4B的放置在焊膏上的导体的示例性焊接和冷却的剖视图。
图4D是示出了通过如例如图1A中所示的示例性过程，接着通过如例如图4A至4C中所示的示例性过程焊接到铝金属化物的导体的一个示例的剖视图。
图5A是示出了铝金属化物和铝金属化物上的铝氧化物层的一个示例的剖视图。
图5B是示出了图1A的铝氧化物层的示例性活化过程的剖视图。
图5C是示出了将焊料沉积物示例性地施加在图5B的铝金属化物之上的剖视图。
图5D是示出了将导体示例性地放置在图5C的焊料沉积物上的剖视图。
图5E是示出了根据图5D的放置在焊料沉积物上的导体的示例性焊接和冷却的剖视图。
图5F是示出了通过如例如图5A至5E中所示的示例性过程焊接到铝金属化物的导体的一个示例的剖视图。
图6是示出了一种导体和铝金属化物焊接在一起的示例性装置的剖视图，其中，导体是芯片载体或夹，铝金属化物是芯片电极。
图7是示出了一种导体和铝金属化物焊接在一起的示例性装置的剖视图，其中，导体是芯片电极，铝金属化物是芯片载体或夹。
具体实施方式
在下面的详细描述中，参考了构成说明书的一部分的附图，所述附图中通过图示示出了一些具体实施例。在这点上，参考所描述的图的取向使用诸如“顶”、“底”、“前”、“后”、“上”、“下”等的方向性术语。因为实施例的构件可以以多个不同的取向定位，所以方向性术语用于说明的目的，而不是限制性的。应当理解，在不脱离本说明书的范围的情况下，可以利用其它实施例并且可以进行结构或逻辑改变。因此，下面的详细描述不应被认为是限制性的。
本说明书中所采用的术语“结合”、“附连”、“连接”、“耦合”和/或“电连接/电耦合”并不意味着元件或层必须直接接触在一起；而是可以在被“结合”、“附连”、“连接”、“耦合”和/或“电连接/电耦合”的元件之间相应地提供插入元件或层。然而，根据本公开，上述术语也可以可选地具有这样的特定含义：即元件或层直接接触在一起，即在被“结合”、“附连”、“连接”、“耦合”和/或“电连接/电耦合”的元件之间没有提供插入元件或层。
此外，这里关于一表面“之上”形成或定位的部件、元件或材料层中使用的词语“在...之上”可以用于可选地表示部件、元件或材料层被“直接”定位(例如放置、形成、沉积等)“在所述表面上”，例如与所述表面直接接触。这里关于在一表面“之上”形成或定位的部件、元件或材料层中使用的词语“在...之上”也可以用于表示所述部件、元件或材料层被“间接地”定位(例如放置、形成、沉积等)在所述表面上而在所述表面与部件、元件或材料层之间布置一个或两个以上附加的部件、元件或层。
此外，这里在两个或两个以上构件的相对取向方面可以使用诸如词语“垂直”和“平行”等的几何术语。应当理解，这些术语可能不一定必然意味着指定的几何关系是以完美的几何意义来实现的。相反，在这点上可能需要考虑相关构件的制造公差。例如，如果半导体封装体的包封材料的两个表面被指定为彼此垂直(或平行)，则这些表面之间的实际角度可以以一偏差值偏离90(或0)度的精确值，所以偏差值可能特别是与在应用用于制造由包封材料制成的壳体的技术时通常可能发生的公差有关。
此外，“X合金”(包括另外的组分Y、Z、......)意味着X按％重量的含量分别大于Y按％重量的含量和Z按％重量的含量。特别地，它可能意味着X的贡献为至少50％重量。
符号XY指的是X合金，其至少包括Y作为另外的组分。特别地，它可以指包含Y作为唯一残余组分的X合金。
本文所描述的方法的实施例可以用于焊接半导体器件，例如半导体芯片，所述半导体器件具有到铝衬底的导电电极。此外，本文所描述的方法的实施例可以用于将半导体器件铝金属化物、例如芯片铝电极焊接到金属衬底，其中，金属衬底可以包括或由例如铜、铜合金、铝、铝合金等制成。
如本领域中所已知的，铝金属化物被高度稳定的Al2O3层涂覆。Al2O3具有自由生成焓DGf0＝-1582.3kJ/mol。这种高度稳定的氧化物通过含有通常用于半导体焊接的助焊剂(例如以松香或其它有机酸、例如丙二酸或草酸为基础的低活性的助焊剂)的焊膏来保护铝免受焊料的侵蚀。高度稳定的Al2O3层可以通过高反应性的化学物质、例如与H2SO4混合的HCl或HF去除。然而，这些高反应性的化学物质不能应用于半导体加工。
此外，由于Al2O3在裸铝上的高的形成率，所以裸铝表面仅在短时间段内是稳定的。这通常还需要使用高活性的助焊剂或带有氯离子和氟离子的特定盐混合物。然而，这些物质的参与在半导体器件中造成高腐蚀风险，因此，在半导体应用中尚未被认为是可能的。
图1A至1I示出了根据本公开的第一方面的将导体焊接到铝金属化物的方法的各种实施例的多个阶段。参考图1A，铝金属化物110被铝氧化物层120覆盖。铝氧化物层120可以包括Al2O3或者可以是Al2O3。如上所述，铝金属化物110可以例如是半导体芯片电极或衬底或芯片载体、例如引线框架，或者是衬底或芯片载体上的金属化物、例如PCB(印刷电路板，Printed Circuit Board)上的金属化物或陶瓷衬底上的金属化物。
此外，应当指出的是，铝金属化物110不需要仅为铝，而是可以是铝合金，即可以包含例如Si和/或Cu和/或Mg和/或SiCu和/或其它元素的成分。例如，铝金属化物110可以是AlSiCu合金，其含有例如0％重量≤Cu≤5％重量和0％重量≤Si≤1％重量。举例来说，铝金属化物110可以是98.5Al-1Si-0.5Cu(即98.5％重量的Al、1％重量的Si、0.5％重量的Cu)铝合金。这种铝合金，特别是AlMg、AlSi、AlCu或AlSiCu，在本文中也将被称为“铝金属化物”。
铝氧化物层120可以具有几纳米的厚度，例如，厚度最高可达2纳米或厚度最高可达5纳米。这种厚度的铝氧化物层120形成非常稳定的钝化层，所述钝化层不能容易地经由常规的酸处理去除。
在下文中，公开了如何用不太稳定的金属氧化物或金属合金氧化物替代Al2O3层而不对半导体器件(例如半导体芯片)产生腐蚀性影响的多种可能性。
根据多个实施例，用替代金属或替代金属合金氧化物层替代铝金属化物上的铝氧化物层的过程可以包括活化。图1B示意性地示出了用于活化铝氧化物层120的几个示例。活化铝氧化物层120可以具有降低铝氧化物层120的稳定性的意义。特别地，活化铝氧化物层120可以具有部分地或完全地去除先前形成的铝氧化物的意义。活化铝氧化物层120的过程是可以在多个实施例中省略的可选的过程。
活化铝氧化物层120的可能性可以包括将HF(氢氟酸)和MSA(甲磺酸)中的一种或两种以上施加到铝氧化物层120。举例来说，可以施加纯MSA或HF和MSA的混合物。HF和/或MSA的施加由箭头Ac表示。举例来说，在含水溶液中HF和MSA的混合物可以直接沉积在铝氧化物层120的上(暴露的)表面120a上。氟离子可以与上表面120a处的铝氧化物层120形成复合物并且最后还可以形成AlF3，所述AlF3稍后可以在酸性溶液中溶解。Al2O3随HF和/或MSA的溶解降低了铝(Al2O3)层120的稳定性。
(可选地)活化铝氧化物层120以降低其稳定性的另一可能性包括经由RF(射频，Radio Frequency)等离子体工艺将氟施加到铝氧化物层120。Ar和CF4气体的混合物可以被用于等离子体过程中。在该过程中，氟被掺入到铝氧化物层120中。更具体地，铝氧化物层120可以在等离子体过程中形成AlF3。如上所述，氟化的铝氧化物层120具有降低的稳定性并且可以例如之后溶解。
施加氟以(可选地)活化铝氧化物层120来降低其稳定性的上述概念可以概括为掺入卤化物，例如F、Cl、Br和I中的一种或两种以上的概念，以通过使铝氧化物层120变弱来活化铝氧化物层120。
多种可能性是可用的，并且可以例如在需要时组合使用：
(1)用含碳氟化合物的等离子体(例如CHF3、C2F2、CH3F或CF4气体或例如还混合有Ar、He、O2、H2或H2O中的一种或两种的气体混合物)等离子体处理Al2O3。同样，F可以被其它卤化物替代。
(2)用其它氟或氯化合物等离子体，例如SF6、CHCl3、CH2Cl2、CH3Cl、CCl3等离子体处理Al2O3。
(3)用溴化或碘化有机分子等离子体处理Al2O3，使得这些卤素掺入到Al2O3层中，从而使该层变弱。
在用卤化物基的等离子体等离子体处理Al2O3期间，形成特定的氟氧化铝混合物，所述氟氧化铝混合物不太稳定并且可以在下面进一步描述的条件下用标准焊剂-焊膏或甚至焊丝焊接。可以用俄歇深度剖面测量Al2O3层中的卤化物(例如氟基)的常用含量。以氟为例，在溅射时间于F最大峰值处观察到F/O原子浓度比例如约为0.5。已经观察到沿着Al2O3层厚度处于0.01与10之间的最大F含量(或通常，卤素含量)的原子浓度比，并且由于弱化的Al2O3层，可以适合于铝的焊接。如下面将进一步解释的，用卤化物基的等离子体处理(活化)Al2O3也可以用作“独立”过程，其中，掺入卤素的Al2O3被直接焊接。这里“独立”意味着，在这种情况下可能不需要通过用另一种金属或金属合金替代铝的过程来转化Al2O3层。
所有这些用于活化铝氧化物层120的方法(即，在含水溶液中施加HF/MSA、在RF等离子体过程中施加Ar/CF4气体混合物以及将卤素或卤化物掺入到铝氧化物层120中)可以组合。此外，还可以添加对铝金属化物110进行预处理以使其上的铝氧化物层120的稳定性变弱的附加过程。
参考图1C，然后，用替代金属氧化物层130或替代金属合金氧化物层130替代(例如活化的)铝氧化物层120。该替代层在本文中将被称为替代金属或替代金属合金氧化物层130。
用于形成替代金属或替代金属合金氧化物层130的替代金属可以例如是Zn、Cr、Cu、Pb或Sn。这些金属可以用于以更低的自由生成焓替代Al2O3。举例来说，在下表中给出一些替代金属氧化物的生成焓DGf0。
金属氧化物 DGf0[kJ/mol]
ZnO -300
CuO -146
Cu2O -129.7
PbO -189.93
PbO2 -217.33
SnO -256.9
SnO2 -438.2
这些金属氧化物可以由低活性的助焊剂溶解，并且可以在还原气氛中在焊接过程中还原成它们的金属状态。
特别地，当形成Zn或Cr的替代金属合金氧化物层时，替代金属合金可以包括元素Zn、Cr、V和Mo中的至少两种。更具体地，替代金属或替代金属合金可以由Zn、Cr、ZnCr、CrZn中的一种及其包括V和Mo中的一种或两种以上的合金组成。
替代可以包括在(例如先前活化的)铝氧化物层120之上沉积替代金属或替代金属合金。根据第一种可能性，可以使用电化学沉积工艺。该电化学沉积工艺可以包括电化学电池的使用，该电化学电池包括阴极、阳极和用于电极之间的电解质的隔室。举例来说，可以使用碱性电解质。
在下文中，在不失一般性的情况下，Zn将被用作替代金属的一个示例。然而，在此的公开内容类似地包括其它金属或金属合金，例如，作为替代金属的一个示例的Cr。
例如，可以在(例如先前活化的)铝氧化物层120之上沉积裸Zn层。可以使用的碱性电解质例如是含有氰化物或不含氰化物的
Figure BDA0001748717120000091
替代性地，酸性或中性电解质，例如ZnSO4或ZnCl2基电解质、带有/>
Figure BDA0001748717120000093
的ZnSO4、没有/>
Figure BDA0001748717120000092
的ZnSO4、带有NH4Cl的Zn2+等也可以用于施加裸Zn层。
这些或其它裸Zn基电解质还可以包括添加剂，例如铬酸盐(Cr)和/或钒酸盐(V)和/或钼酸盐(Mo)。在这些情况下，可以通过电化学沉积将ZnCr和/或ZnV和/或ZnMo金属合金层作为替代金属合金沉积在铝氧化物层120之上。对于ZnCr和/或ZnV和/或ZnMo合金层沉积，也可以使用碱性电解质。在这种情况下，碱性电解质含有Cr离子和/或V离子和/或Mo离子，并且可以展示出Cr和/或V和/或Mo与Zn一起的反常共沉积特性。ZnCr和/或ZnV和/或ZnMo合金层的Cr和/或V和/或Mo含量可以等于或高于1％重量、特别是5％重量，并且可以等于或小于40％重量，其余为Zn且可选地，较小含量的其它元素、例如Si等。
举例来说，为了沉积ZnCr合金层，可以使用包括或由12g/L NaOH、0.9g/L Zn2+、0.6g/L Cr6+和可选的70ppm Si4+组成的电解质。ZnCr合金层可以含有六价Cr。
Zn金属层或ZnCr和/或ZnV和/或ZnMo金属合金层可以具有等于或大于1.5、10、20、40、60或80纳米的厚度。Zn金属层或ZnCr和/或ZnV和/或ZnMo金属合金层可以具有等于或小于100、80、40、20、10或5纳米的厚度。
在铝氧化物层120之上沉积替代金属或替代金属合金的第二种可能性是使用无电沉积工艺。无电沉积工艺可以包括在不施加电流的情况下将铝氧化物层120的上表面120a化学暴露于电解质。举例来说，可以使用所有上述电解质，并且可以应用上述的所有替代金属或替代金属合金(例如裸Zn或ZnCr、ZnV、ZnMo合金)。化学暴露可以例如通过在电解质池中的铝金属化物110的浸蘸工艺获得。举例来说，铝金属化物110(连同其上的铝氧化物层120)可以浸入到电解质中约15至60秒。
上述所有示例性工艺使得用替代金属或替代金属合金氧化物层130替代了铝氧化物层120。通过沉积Zn或ZnCr或ZnV或ZnMo层替代Al2O3层120，分别形成ZnO、ZnCr-氧化物、ZnV-氧化物或ZnMo-氧化物。随着这些新氧化物的形成和Al2O3的消失，由于ZnO或ZnCr-/ZnV-/ZnMo-氧化物与Al2O3相比在热力学上不太稳定，因此在随后的加工期间可以更容易地还原替代铝氧化物层120的层(即替代金属或替代金属合金氧化物层130)。如下面将进一步更详细描述的，这种稳定性的降低可以促进或者已经允许随后在铝金属化物110上的焊接。
应当指出的是，由替代金属或替代金属合金氧化物层130替代铝氧化物层120伴随着层的结构和形态变化。更具体地，替代金属或替代金属合金氧化物层130可以具有海绵状的、多孔的、树枝状的或其它不均匀的结构。
在下文中，描述了替代过程的一些具体示例(可选地包括活化)。这些示例可以与如上所述的活化和/或沉积的特征组合。
示例A：替代可以包括HF/MSA活化和用沉积1-100纳米厚的ZnCr合金层的碱性电解质的镀覆工艺。附加性地或替代性地，电解质可以用于施加裸Zn层。
示例B：在可选的HF/MSA活化之后，可以使用使用裸锌酸盐或锌酸盐与钒酸盐或钼酸盐(代替铬酸盐，参见示例A)的电解质的无Cr电解质。
示例C：可以在示例A和示例B中提到的每种电解质中进行浸蘸过程以进行替代。浸蘸是铝氧化物表面对所用的相应电解质的短(例如1至120秒)暴露，接着是可选的HF/MSA活化、不施加电流的Cr-溶液中的一种。在浸蘸过程中，铝氧化物被相应的Zn或Zn合金层替代。
示例D：可以使用将替代金属掺入到铝氧化物层中的等离子体工艺(例如，上文所述)。为此，可以将金属有机分子气体添加到等离子体中并将其用作替代金属的来源，以形成“软替代金属氧化物”。
示例E：可以使用溅射工艺将替代金属溅射到Al2O3层上，以便在Al2O3与金属氧化物之间得到混合氧化物，例如AlCu氧化物或AlZn氧化物。
参考图1D，替代金属或替代金属合金氧化物层130至少部分地被还原。至少部分地还原该层的第一种可能性是在升高的温度下施加还原气体，以还原替代金属或替代金属合金氧化物层130的替代氧化物(例如ZnO和/或ZnCr-氧化物和/或ZnMo-氧化物和/或ZnV-氧化物等)。还原性气体的施加在图1D中用箭头Rg表示。
当施加还原气体时，根据第一示例，可以使用包含H2和惰性气体、例如N2的混合物的所谓的合成气体作为还原气体。在下文中，在不失一般性的情况下，将N2作为惰性气体的一个示例。
合成气体N2/H2可以具有浓度在0.001％至10％的范围内的H2。特别地，可以使用N2/5％H2合成气体。
还原气体在施加到替代金属或替代金属合金氧化物层130时的升高的温度可以在150℃至500℃之间的范围内。更具体地，还原气体Rg的升高的温度可以等于或小于或大于500℃、450℃、400℃、380℃、350℃、330℃、300℃、270℃、250℃、220℃或200℃。特别地，可以使用330℃±30℃的温度。
还原气体Rg的压力可以在10-5Pa至107Pa之间的范围内。特别地，可以使用在例如10-4Pa至10-2Pa的范围内的约10-3Pa的压力。举例来说，在压力10-3Pa、温度330℃的条件下，ZnO已经由N2/5％H2还原。
根据第二示例，还原气体Rg可以包括惰性气体(例如N2)和CH2O2(甲酸)的混合物。在惰性气体中，可以使用浓度在0.01％至10％之间的范围内的CH2O2。特别地，可以在N2中使用3％甲酸的浓度。
可以在相同范围内或甚至低于针对施加N2/H2合成气体所述的温度的温度下施加N2/CH2O2的还原气体Rg。N2/CH2O2还原气体Rg的施加压力可以与针对N2/H2合成气体所述的压力范围相同。举例来说，在10-3Pa的压力下，即使在等于或小于250℃的较低温度下，ZnO也可由N2/CH2O2还原。
还可以在与上述相同的温度和/或压力范围内施加上述还原气体Rg的混合物(即在惰性气体中的H2和CH2O2的混合物)。
可以施加的其它还原气体是乙醇、丙酮、丙醇、乙烯和同系物、乙炔和同系物或其它可以在表面上形成活性(还原)氢使得形成例如裸金属表面的挥发性物质。对于这些其它还原气体，适用如上所述的相同的压力和/或温度范围。
用于还原替代金属或替代金属合金氧化物层130中的替代金属氧化物或替代金属合金氧化物的还原气体Rg的施加可以可选地通过施加RF(射频)等离子体或微波等离子体(MW：MicroWave plasma)来增强。例如，还原气体或自由基也可以来自在化学物中或RF等离子体中用H2或含H的气体(例如CHF3、CH2F2、CH3F、CH4等、或其气体混合物)等离子体处理不太稳定的金属氧化物。
更具体地，图2示出了上述两种还原气体Rg中的各种金属氧化物的计算出的以H2O的Pa为单位的平衡压力p与以K为单位的温度的关系。在N2中的H2的合成气体中的平衡反应是
Al2O3+3H2<＝>2Al+3H2O
Cr2O3+3H2<＝>2Cr+3H2O (1)
ZnO+H2<＝>Zn+H2O
在N2中的CH2O2的还原气体中的平衡反应是
Al2O3+3CH2O2<＝>2Al+3H2O+3CO2。 (2)
从图2中可以看出，在N2/H2中ZnO和Cr2O3的还原温度显著低于在N2/H2中Al2O3的还原温度，即前述替代金属氧化物的热力学稳定性显著小于氧化铝的热力学稳定性。此外，图2还示出了CH2O2在还原氧化铝方面比H2更有效。尽管在图2中仅示出了CH2O2对氧化铝的较高效率，但它也适用于替代金属氧化物(即ZnO和/或Cr2O3等)的还原。此外，图2还示出了替代金属氧化物的还原已经可以在半导体加工过程中容易地施加的温度下进行。
参考图1E，替代金属或替代金属合金氧化物层130中的替代金属氧化物的还原生成(氧化物还原生成的)替代金属或替代金属合金层140。该(氧化物还原生成的)替代金属或替代金属合金层140将不再含有ZnO和/或替代金属的其它氧化物。如下面将进一步描述的，通过例如使用还原气体Rg的还原可以使得能够焊接铝金属化物110而不必使用高活性的助焊剂或者甚至不必使用任何助焊剂。另外，这使得铝金属化物110的焊接通常在活化/替代处理期间受到最小的腐蚀侵蚀的影响，因为在例如电化学沉积替代金属(例如Zn或Zn合金)期间经由Al2O3的溶解活化了铝。在这种情况下，用“软金属氧化物”对Al2O3的侵蚀和替代附加性地由阴极处的沉积电流支持。
图1F至1I示出了当被如例如通过图1D的还原过程产生的(氧化物还原产生的)替代金属或替代金属合金层140覆盖时将导体150焊接到铝金属化物110的示例性过程的多个阶段。
根据图1F，焊料沉积物160被沉积在铝金属化物110之上。更具体地，焊料沉积物160被施加到(氧化物还原产生的)替代金属或金属合金层140。
焊料沉积物160的施加可以通过标准焊料附连工艺来执行。焊料沉积物160包括焊料材料并且可以包括助焊剂。焊料材料可以例如含有Pb。举例来说，可以使用PbSnAg焊料。举例来说，可以使用95.5Pb-2Sn-2.5Ag焊料(即具有95.5％重量Pb、2％重量Sn和2.5％重量Ag的组分的焊料)或SnAgCu焊料或Sb-Sn焊料或者任何其它常规用于半导体芯片焊接的标准焊料。
对铝金属化物110的焊接用作为一种成分包含在焊料材料中以通过形成金属间相与铝反应的金属进行。与铝发生反应的金属是例如Cu、Ni、Ti、V、Zn、Fe、Ta和/或W(然而，Sn不与铝发生反应)。这些金属(即与铝形成金属间相的金属)可以通过各种方式提供：
根据一种可能性，这种或这些金属可以作为一种成分包含在导体150(即待焊物)、例如夹的材料中。根据另一种可能性，金属可以在焊料材料中被合金化为混合物。此外，金属还可以由焊料材料中的金属颗粒提供。此外，金属还可以经由将金属镀覆在焊丝上或者通过提供金属有机分子形式的金属作为助焊剂的一部分来提供。
可以组合上述如何施加金属以用于金属间相的可能性。举例来说，焊料材料的组成可以包含形成或包含在导体150中的金属成分。如果导体150的面向焊料沉积物160的表面包括或者是例如Cu、Ni、Cu/Ni、NiP、Ni/NiP或其合金，则焊料材料也可以包含Cu、Ni、Cu/Ni、NiP、Ni/NiP或其合金的成分。
作为另一个示例，使用95.5Pb-2Sn-2.5Ag焊料和由Cu与Cu-Fe-P合金组成的导体150(例如，夹)。
在焊接过程中可以使用标准的低活化的助焊剂(其不是极度腐蚀性的)或不使用助焊剂。特别地，不需要使用高活化的助焊剂，例如用于Al2O3还原的助焊剂。而是，通过铝氧化物层120的溶解来活化铝金属化物110是在铝氧化物层120上电化学沉积或无电沉积替代金属或替代金属合金期间完成的，参见图1B。这种替代金属或替代金属合金沉积活化具有最小的腐蚀侵蚀的影响，因此，如本文所考虑的那样，在半导体器件制造中，使在铝金属化物110上进行焊接成为可能。
可以在真空焊接炉(未示出)中执行焊料沉积物160的施加。例如，焊料沉积物160可以以焊膏的形式分配在铝金属化物110之上。
应当指出的是，可以在同一个焊接炉中完成焊料沉积物160(参见图1F)的施加和上述还原替代金属氧化物的过程。特别地，焊接工艺可以在用于氧化物还原过程的还原气体Rg气氛中执行。通常，当使用还原气体Rg时，可以在将导体焊接到铝金属化物110的过程之前或在将导体焊接到铝金属化物110的过程期间执行至少部分地或完全地还原替代金属氧化物或替代金属合金氧化物层130中的替代金属氧化物的过程。
图1G示出了导体150到液态焊料沉积物160的放置。然后，焊料沉积物160可以冷却到例如50℃到80℃并且在该过程期间固化(图1H)。
图1I示出了装置100，其包括通过固化的焊料层160'结合到铝金属化物110的导体150。固化的焊料层160'可以直接接触(氧化物还原的)替代金属或替代金属合金层140。这样，导体150被机械地固定并电连接到铝金属化物110。
根据至少部分地还原替代金属或替代金属合金氧化物层130的第二种可能性，可以省略通过施加还原气体Rg还原替代金属氧化物的过程(图1D)。而是，替代金属氧化物的还原可以在随后的焊接过程中进行。该过程将在下面参考图3A至3D示例性地描述。
在这种情况下，根据图3A，焊料沉积物160被施加到铝金属化物110。然而，更具体地，焊料沉积物160被施加到(图1C的)替代金属或替代金属合金氧化物层130而不是图1E的(氧化物被还原的)替代金属或替代金属合金层140。也就是说，没有执行替代金属或替代金属合金氧化物还原(图1D)。
焊料沉积物160的施加可以通过标准焊料附连工艺来执行。焊料沉积物160包括焊料材料并且可以包括助焊剂。焊料材料可以例如含有Pb。特别地，可以使用与上面结合图1F所述相同的PbSnAg焊料。
举例来说，可以使用95.5Pb-2Sn-2.5Ag焊料(即具有95.5％重量的Pb、2％重量的Sn和2.5％重量的Ag的成分的焊料)或SnAgCu焊料或Sb-Sn焊料或任何其它标准焊料和传统用于半导体芯片焊接的标准低活化的助焊剂。这里也可以使用的半导体焊接中所用的常用的助焊剂被低活化并且基于树脂(松香)或其它有机酸、例如丙二酸或草酸。焊接也可以作为焊丝或焊料预制件基的焊接工艺或者使用助焊剂或者在还原气氛中完成。
此外，在金属间相形成的情况下，可以使用与上述相同的焊料材料的组成和/或导体150的组成。焊料材料可以包含形成或包含在导体150中的金属成分。参考上面的相应公开内容。
焊料沉积物160的施加可以在真空焊接炉(未示出)中执行。例如，焊料沉积物160可以以焊膏的形式分配在铝金属化物110之上。
用于半导体器件焊接的标准低活化的助焊剂(即不具有极度腐蚀性的助焊剂)可以用于焊接过程中。特别地，不需要使用高活化的助焊剂。如上面已经描述并在此提到的，通过铝氧化物层120的溶解来活化铝金属化物110已经在(即在铝氧化物层120上电化学沉积或无电沉积替代金属或替代金属合金期间产生的，参见图1B)先前处理期间执行。
通过焊料沉积物160与替代金属或替代金属合金氧化物层130的直接接触来还原替代金属氧化物(例如ZnO和/或Cr2O3等)。更具体地，具有例如与图1E中的(氧化物被还原的)替代金属或替代金属合金层140相同的组成的(氧化物被还原的)替代金属或替代金属合金层区域140_1由焊料沉积物160与替代金属或替代金属合金氧化物层130接触或重叠的区域中的替代金属或替代金属合金氧化物层130生成。在重叠区域的横向外侧，替代金属或替代金属合金氧化物层130的替代金属氧化物不被还原，即(氧化物被还原的)替代金属或替代金属合金层区域140_1可以被替代金属或替代金属合金氧化物层130的未改变区域130_1包围(图3B)。
图3B进一步示出了导体150到液态焊料沉积物160的放置。然后，焊料沉积物160可以冷却到例如50℃到80℃并在该过程期间固化，如结合图1H所描述的。
图3C和3D分别对应于图1H和1I，参考上面的描述以避免重复。在导体150通过固化的焊料层160'机械地固定并电连接到铝金属化物110的情况下，图1D至1I(通过施加还原气体Rg的整个氧化物还原)与图3A至3D(通过与焊料沉积物160接触的局部氧化物还原)中所示的过程之间的差异在最终装置300中通过提供替代金属或替代金属合金氧化物层130的未改变区域130_1而保持可检测的。也就是说，(氧化物被还原的)替代金属或替代金属合金层区域140_1被限制在与固化的焊料层160'相同形状的区域中，并被替代金属氧化物或替代金属合金氧化物层的未改变区域130_1包围。固化的焊料层160'可以直接接触(氧化物被还原的)替代金属或替代金属合金层区域140_1。
根据本公开的第二方面，如通过图4A至4D中的示例所示，不需要在铝金属化物110上调理或活化铝氧化物层120。取而代之的是，可以通过将助焊剂材料施加到铝金属化物110上的铝氧化物层120并且通过将焊料材料沉积在铝金属化物之上来达到铝氧化物的去除，其中，焊料材料具有大量的Zn。更具体地，焊料材料的化学组成可以是x％重量≤Zn≤100％重量，其中x＝10、30、50、70、90、95或100。
焊料材料的其余化学组成可以包含Al、Cu、Ni、Ti和可选的如上所述的残余组分中的一种或两种以上。特别地，可以使用主要或仅由Zn和Al组成的焊料材料(即ZnAl或AlZn或其具有上述组成的合金)。Zn含量越高，焊料材料在从铝金属化物中去除铝氧化物、即在焊接过程中与助焊剂材料一起还原铝氧化物方面就越有效。
为了防止任何卤化物催化的腐蚀，还添加了其它分子以有效地溶解Al2O3。第一种可能性是向助焊剂材料中添加硅酸盐，例如特定的硅酸盐，例如沸石。举例来说，可以添加相对于助焊剂含量为0.01％重量至10％重量的浓度范围内的硅酸盐(或沸石)。硅酸盐(或沸石)可有效降低助焊剂材料的腐蚀性影响。
例如，助焊剂材料可以是至少有助焊剂和硅酸盐(沸石)的混合物，助焊剂材料具有x％重量≤硅酸盐和/或硅酸盐≤x％重量的化学组成，其中x＝0.1、0.5、1.0、2.0、4.0、6.0或8.0。助焊剂材料的其余化学组成可以是能够还原Al2O3的(被高度活化的)助焊剂。
经由卤化物降低腐蚀性影响的另一种可能性是向助焊剂中添加冠醚。举例来说，可以添加相对于助焊剂含量为0.01％重量至50％重量的浓度范围内的冠醚。举例来说，助焊剂材料可以是至少有助焊剂和冠醚的混合物，助焊剂材料具有x％重量≤冠醚和/或冠醚≤x％重量的化学组成，其中x＝0.1、0.5、1.5、10、20、30或40。助焊剂材料的其余化学组成可以是能够还原Al2O3的(被高度活化的)助焊剂。
可以组合这两种降低助焊剂材料的腐蚀性影响的措施(即向助焊剂中添加硅酸盐(例如沸石)和向助焊剂中添加冠醚)。硅酸盐(例如沸石)和/或冠醚可以有助于最小化腐蚀，因为它们可以在焊接过程期间和在焊接过程之后捕获阴离子和阳离子。此外，除了硅酸盐和冠醚之外，其它铝络合剂可以相对于助焊剂含量以0.01％重量至10％重量的浓度范围添加到助焊剂中。
通过例如上述措施中的一种或两种以上措施减少助焊剂材料的腐蚀性影响，从而允许在用于半导体器件焊接的助焊剂材料中使用高度活化的助焊剂。
参考图4A，焊膏460被施加在铝金属化物110之上。铝金属化物110仍然包括铝氧化物层120。可以应用与结合图1F描述的相同的施加/分配过程。助焊剂材料和焊料材料可以例如在施加之前已经混合在一起以形成焊膏460。焊料材料可以具有如上所述的组成，助焊剂材料可以具有如上所述的组成。
在施加期间或在施加之后，加热焊膏460并将导体150放置在焊膏460上(图4B)。可以应用与结合图3A和3B描述的类似过程，并且参考上述的公开内容。特别地，焊接过程可以通过施加还原气体和/或通过施加RF等离子体获得支持，如结合图1D至1G所描述的。如上所述，导体150的放置(图4B)和焊接(图4C)可以例如在隧道炉(未示出)中执行。
仍然参考图4B，通过焊膏460与铝氧化物层120的直接接触来还原铝氧化物层120的铝氧化物。更具体地，(氧化物被还原的)铝区域420_1是由在焊膏460与铝氧化物层120接触或重叠的区域中的铝氧化物层120生成的。在重叠区域的横向外侧，铝氧化物层120未被还原，即(氧化物被还原的)铝区域420_1可以被铝氧化物层120的未改变区域120_1包围(图4B)。
如上所述，铝金属化物110可以由裸铝或铝合金组成。特别地，可以使用铝合金98.5Al-0.5Cu-1Si或99Al-1Si正面金属化物。待焊接到铝金属化物110的导体150可以包括或者可以是与上述相同的材料，例如Cu、Ni、Cu/Ni、NiP、Ni/NiP或其合金。这些物质是指导体150的表面区域的组成，其有效地提供了有助于在焊接期间生成的金属间化合物的材料。金属间化合物是在焊接过程中由焊料材料与导体的表面区域和铝金属化物110(或者更具体地，(氧化物被还原的)铝区域420_1)的反应生成的。
然后，焊膏460被冷却以固化并提供机械和电连接。参考图1H、1I和3C、3D的描述，其可以分别相同地适用于图4C和4D所示的过程，但除了没有在固化的焊膏460'与铝金属化物110之间提供中间(氧化物被还原的)替代金属或替代金属合金层140(参见图1H、1I)或(氧化物被还原的)替代金属或替代金属合金层区域140_1(图3C、3D)外。相反，固化的焊膏460'可以直接连接到铝金属化物110(经由厚度仅为几纳米的(氧化物被还原的)铝区域420_1)。
图4D是示出了装置400的一个示例的剖视图，所述装置400包括通过如例如图1A中所示的示例性过程，接着通过如例如图4A至4C中所示的示例性过程焊接到铝金属化物110的导体150。
图5A至5F示出了根据本公开的第三方面的将导体焊接到铝金属化物的方法的各种实施例的多个阶段。根据本公开的第三方面，不需要通过如针对本公开的第一方面所述的用另一种金属或金属合金替代铝的过程来转化Al2O3层。
参考图5A，铝金属化物110被铝氧化物层120覆盖。参考图1A的描述以避免重复。
图5B示意性地示出了用于活化铝氧化物层120的多个示例。活化铝氧化物层120可以具有降低铝氧化物层120的稳定性的意义。这里，通过将卤化物经由等离子体工艺施加到铝金属化物110上的铝氧化物层120来执行铝氧化物层120的活化，以产生卤化铝氧化物层540(参见图5C)。也就是说，用于降低铝氧化物层120的稳定性的对铝氧化物层120的活化(AC)可以通过掺入卤化物，例如F、Cl、Br和I中的一种或两种以上来实现。
多种可能性是可用的，并且可以例如在需要时组合：
(1)用含碳氟化合物的等离子体(例如CHF3、C2F2、CH3F或CF4气体或例如还与Ar、He、O2、H2或H2O中的一种或两种以上混合的气体混合物)等离子体处理Al2O3。同样，F也可以被其它卤化物替代。
(2)用其它氟或氯化合物等离子体，例如SF6、CHCl3、CH2Cl2、CH3Cl、CCl3等离子体处理Al2O3。
(3)用溴化或碘化有机分子等离子体处理Al2O3，使得这些卤素掺入到Al2O3层中，从而使该层变弱。
在用卤化物基的等离子体等离子体处理Al2O3期间，形成特定的铝-氟氧化物的混合物，所述铝-氟氧化物的混合物不太稳定并且可以用标准助焊剂-焊膏或甚至焊丝焊接。标准助焊剂-焊膏可以是含有通常用于半导体焊接中的助焊剂、例如基于松香或其它有机酸(例如丙二酸或草酸)的被低活化的助焊剂的焊膏。
如已经提到的，Al2O3层中的卤化物(例如氟基)的常用含量可以用俄歇深度剖面来测量。以氟为例，在溅射时间上的F最大峰值处观察到F/O原子浓度比例如约为0.5。已经观察到沿着Al2O3层厚度在0.01与10之间的最大F含量(或通常，卤素含量)下的原子浓度比，并且由于弱化的Al2O3层，其可以适合于铝的焊接。
与如结合图1B所述的(可选的)活化不同，根据本公开的第三方面，用卤化物基的等离子体处理(活化)Al2O3被用作“独立”过程。这里“独立”是指不使用通过另一种金属或金属合金替代铝的过程来转化Al2O3层。而是，直接焊接卤化铝氧化物层540(即具有掺入的卤素的Al2O3层)。
图5C至5F示出了将导体150焊接到铝金属化物110以制造装置500的一个示例性过程的多个阶段。除了用卤化铝氧化物层540替代(氧化物被还原的)替代金属或替代金属合金层140之外，图5C至5F分别对应于图1F至1I，参考以上描述以避免重复。
通常，焊接可以在铝芯片金属化物(芯片电极)上和/或铝导体，例如芯片载体和/或夹上进行。图6示出了一种导体150和铝金属化物110焊接在一起的示例性装置600。在该示例中，铝金属化物110由半导体芯片610的第一电极611形成，导体150由芯片载体620，例如引线框架形成。半导体芯片610可以例如是具有例如垂直结构的功率器件。半导体芯片610的第一电极611可以例如是半导体芯片610的漏极电极(漏极朝下取向)，或者也可以是半导体芯片610的源极电极(源极朝下取向)。
进一步参考图6，待焊接到铝金属化物110的导体150可以是夹630，并且铝金属化物110可以再次是芯片电极，例如第二芯片电极612。第二芯片电极612可以是半导体芯片610的源极电极(漏极朝下取向)或漏极电极(源极朝下取向)。
可以随后或同时完成半导体芯片610与芯片载体620(150)的焊接和/或夹630(150)的焊接。可以应用任何上述过程、材料、技术等。特别地，上述针对将导体150焊接到铝金属化物110的所有装置100、300、400、500可以应用于用于半导体芯片610的电极611(110)和/或612(110)与芯片载体620(150)的焊接和/或夹630(150)的焊接的装置500中。
根据图7中描绘的另一种可能性，示例性装置700可以包括芯片电极611和/或612，其代表导体150并且由例如上述导体150的材料中的一种或两种以上制成。在这种情况下，芯片载体620，例如引线框架提供铝金属化物110和/或夹630提供铝金属化物110。同样，源极朝下或漏极朝下取向是可能的并且半导体电极611和612都可以随后或同时焊接到芯片载体620(110)和夹630(110)。特别地，上述用于将导体150焊接到铝金属化物110的所有装置100、300、400、500可以应用于用于半导体芯片610的电极611(150)和/或612(150)与芯片载体620(110)的焊接和/或夹630(110)的焊接的装置700中。
虽然本文已经示出和描述了特定实施例，但是本领域普通技术人员将会理解，在不脱离本公开的范围的情况下，各种替代的和/或等同的实施方案可以替代所示的和所描述的特定实施例。本申请旨在涵盖本文所讨论的特定实施例的任何修改或变化。

Claims (50)

1.一种将导体焊接到铝金属化物的方法，所述方法包括：
用替代金属氧化物层或替代金属合金氧化物层替代所述铝金属化物上的铝氧化物层；
至少部分地还原所述替代金属氧化物层中的或所述替代金属合金氧化物层中的替代金属氧化物，其中，所述至少部分地还原包括在升高的温度下将还原气体施加到所述替代金属氧化物层或所述替代金属合金氧化物层；以及
使用焊料材料将所述导体焊接到所述铝金属化物上。
2.根据权利要求1所述的方法，其中，所述替代金属氧化物层的替代金属是Zn、Cr、Cu、Pb和Sn中的一种。
3.根据权利要求2所述的方法，其中，替代包括通过电化学沉积工艺或通过无电沉积工艺在所述铝氧化物层之上沉积所述替代金属。
4.根据权利要求1所述的方法，其中，所述替代金属合金氧化物层的替代金属合金包括Zn、Cr、V、Cu、Pb、Sn和Mo中的至少两种元素。
5.根据权利要求4所述的方法，其中，替代包括通过电化学沉积工艺或通过无电沉积工艺在所述铝氧化物层之上沉积所述替代金属合金。
6.根据权利要求1所述的方法，其中，替代包括将氢氟酸(HF)和甲磺酸(MSA)中的一种或两种施加到所述铝氧化物层。
7.根据权利要求1所述的方法，其中，替代包括经由等离子体工艺将卤化物施加到所述铝氧化物层。
8.根据权利要求1所述的方法，其中，所述还原气体包括H2、CH2O2、乙醇、丙醇、丙酮中的一种或两种以上。
9.根据权利要求1所述的方法，其中，所述升高的温度等于或小于500℃。
10.根据权利要求1所述的方法，其中，所述至少部分地还原包括在将所述导体焊接到所述铝金属化物期间施加低活化助焊剂。
11.一种将导体焊接到铝金属化物的方法，所述方法包括：
用替代金属氧化物层或替代金属合金氧化物层替代所述铝金属化物上的铝氧化物层；
将助焊剂材料施加到所述替代金属氧化物层或所述替代金属合金氧化物层；以及
使用焊料材料将所述导体焊接到所述铝金属化物上。
12.根据权利要求11所述的方法，其中，所述助焊剂材料在将导体焊接到铝金属化物的过程中施加。
13.根据权利要求11所述的方法，其中，所述替代金属氧化物层的替代金属是Zn、Cr、Cu、Pb和Sn中的一种。
14.根据权利要求13所述的方法，其中，替代包括通过电化学沉积工艺在所述铝氧化物层之上沉积所述替代金属。
15.根据权利要求13所述的方法，其中，替代包括通过无电沉积工艺在所述铝氧化物层之上沉积所述替代金属。
16.根据权利要求11所述的方法，其中，所述替代金属合金氧化物层的替代金属合金包括Zn、Cr、V、Cu、Pb、Sn和Mo中的至少两种元素。
17.根据权利要求16所述的方法，其中，替代包括通过电化学沉积工艺在所述铝氧化物层之上沉积所述替代金属合金。
18.根据权利要求16所述的方法，其中，替代包括通过无电沉积工艺在所述铝氧化物层之上沉积所述替代金属合金。
19.根据权利要求11所述的方法，其中，替代包括将氢氟酸(HF)和甲磺酸(MSA)中的一种或两种施加到所述铝氧化物层。
20.根据权利要求11所述的方法，其中，替代包括经由等离子体工艺将卤化物施加到所述铝氧化物层。
21.根据权利要求11所述的方法，其中，所述助焊剂材料包括低活化助焊剂。
22.根据权利要求11所述的方法，其中，所述焊料材料包括PbSnAg、SnAgCu和Sb-Sn中的一种。
23.根据权利要求11所述的方法，其中，所述焊料材料包括Cu、Ni、Ti、V、Zn、Fe、Ta和W中的至少一种。
24.一种将导体焊接到铝金属化物的方法，所述方法包括：
用替代金属氧化物层或替代金属合金氧化物层替代所述铝金属化物上的铝氧化物层；
将助焊剂材料施加到所述替代金属氧化物层或所述替代金属合金氧化物层，以溶解所述替代金属氧化物层中的或所述替代金属合金氧化物层中的替代金属氧化物；以及
使用焊料材料将所述导体焊接到所述铝金属化物上。
25.根据权利要求24所述的方法，其中，所述助焊剂材料在将导体焊接到铝金属化物的过程中施加。
26.一种将导体焊接到铝金属化物的方法，所述方法包括：
用ZnO层替代所述铝金属化物上的铝氧化物层；
将助焊剂材料施加到所述ZnO层；以及
使用PbSnAg焊料材料将所述导体焊接到所述铝金属化物上。
27.根据权利要求26所述的方法，其中，所述助焊剂材料在将导体焊接到铝金属化物的过程中施加。
28.根据权利要求26所述的方法，其中，所述助焊剂材料至少部分还原所述ZnO层中的ZnO。
29.根据权利要求26所述的方法，其中，所述PbSnAg焊料材料包括95.5Pb-2Sn-2.5Ag焊料。
30.根据权利要求26所述的方法，其中，所述PbSnAg焊料材料包括Cu。
31.一种将导体焊接到铝金属化物的方法，所述方法包括：
经由等离子体工艺将卤化物施加到所述铝金属化物上的铝氧化物层，以产生卤化铝氧化物层；
将焊料材料布置在所述卤化铝氧化物层之上；以及
将所述导体焊接到所述铝金属化物上。
32.根据权利要求31所述的方法，其中，所述卤化物包括氟化合物。
33.根据权利要求31所述的方法，其中，所述卤化物包括氯化合物。
34.根据权利要求31所述的方法，其中，所述卤化物选自由CHF3、C2F2、CH3F、CF4、SF6组成的组中的一种或两种以上。
35.根据权利要求31所述的方法，其中，所述卤化物选自由CHCl3、CH2Cl2、CH3Cl和CCl3组成的组中的一种或两种以上。
36.根据权利要求31所述的方法，其中，所述焊料材料包括PbSnAg、SnAgCu和Sb-Sn中的一种。
37.一种将导体焊接到铝金属化物的方法，所述方法包括：
经由等离子体工艺将卤化物施加到所述铝金属化物上的铝氧化物层，以产生卤化铝氧化物层；
将助焊剂材料施加到所述卤化铝氧化物层；
将焊料材料布置在所述卤化铝氧化物层之上；以及
将所述导体焊接到所述铝金属化物上。
38.根据权利要求37所述的方法，其中，所述助焊剂材料在将焊料材料布置在所述卤化铝氧化物层之上的过程中施加。
39.根据权利要求37所述的方法，其中，所述卤化物包括氟化合物。
40.根据权利要求37所述的方法，其中，所述卤化物包括氯化合物。
41.根据权利要求37所述的方法，其中，所述卤化物选自由CHF3、C2F2、CH3F、CF4、SF6组成的组中的一种或两种以上。
42.根据权利要求37所述的方法，其中，所述卤化物选自由CHCl3、CH2Cl2、CH3Cl和CCl3组成的组中的一种或两种以上。
43.根据权利要求37所述的方法，其中，所述焊料材料包括PbSnAg、SnAgCu和Sb-Sn中的一种。
44.一种将导体焊接到铝金属化物的方法，所述方法包括：
经由等离子体工艺将卤化物施加到所述铝金属化物上的铝氧化物层，以产生卤化铝氧化物层；
通过向卤化铝氧化物层施加还原气体至少部分地还原卤化铝氧化物层；
将焊料材料布置在所述卤化铝氧化物层之上；以及
将所述导体焊接到所述铝金属化物上。
45.根据权利要求44所述的方法，其中，所述还原气体包括H2。
46.根据权利要求44所述的方法，其中，所述卤化物包括氟化合物。
47.根据权利要求44所述的方法，其中，所述卤化物包括氯化合物。
48.根据权利要求44所述的方法，其中，所述卤化物选自由CHF3、C2F2、CH3F、CF4、SF6组成的组中的一种或两种以上。
49.根据权利要求44所述的方法，其中，所述卤化物选自由CHCl3、CH2Cl2、CH3Cl和CCl3组成的组中的一种或两种以上。
50.根据权利要求44所述的方法，其中，所述焊料材料包括PbSnAg、SnAgCu和Sb-Sn中的一种。
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