CN1606803A - 制造电子器件的方法 - Google Patents

制造电子器件的方法 Download PDF

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CN1606803A
CN1606803A CNA028254287A CN02825428A CN1606803A CN 1606803 A CN1606803 A CN 1606803A CN A028254287 A CNA028254287 A CN A028254287A CN 02825428 A CN02825428 A CN 02825428A CN 1606803 A CN1606803 A CN 1606803A
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R·A·M·沃特斯
A·M·范格拉文－克拉亚斯森
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Abstract

本发明提供一种在半导体本体上提供铜金属化的方法，包括在含氮气氛中淀积铜以形成含氮铜籽晶层的步骤，以及在籽晶层上形成铜金属化，还包括加热籽晶层以释放氮从而形成将籽晶层与半导体本体隔离的部分阻挡层的步骤。

Description

制造电子器件的方法
本发明涉及一种制造在衬底上具有铜金属化的半导体器件的方法，该铜金属化包括籽晶层和铜金属化层，该方法包括在含氮气氛中淀积铜以形成含氮和铜的籽晶层的步骤，以及在所述籽晶层上形成铜金属化层的步骤。
本发明还涉及一种具有在其上有包括金属氮化物的阻挡层和铜金属化的叠层的衬底的电子器件，该阻挡层和铜金属化具有共同的界面。
通过金属化连接层和通路的方式在集成电路中提供连接是公知的。在半导体工业中越来越盛行的一种金属化材料是铜。然而，发现在铜中存在的缺点是通过各种材料快速扩散，尤其是通过电介质材料，如氧化物。
因此试图采用铜金属化的半导体结构具有用于将铜金属化与下面的半导体本体的材料隔离，并由此防止这种扩散进入本体的阻挡材料。含氮阻挡材料证明是适合的选择，但是在该阻挡层与在随后的铜金属化层的电沉积之前淀积在阻挡层上的铜籽晶层之间可以获得的粘着度方面显示了缺点。在关于通过作为部分该结构而形成的铜金属化轨迹所提供的薄层电阻方面也显示了缺点。
US-A-6174799公开了一种电子器件以及在开始的段落中描述的制备这种电子器件的相应方法。在已知的方法中，该籽晶层包括铜和镁、锡、或铝的合金。在其浓度随籽晶淀积进行而降低的氮气气氛中淀积该籽晶层，以提供显示分级的氮含量的籽晶层。该氮含量的分级使得接近阻挡层的籽晶层区域具有高的氮浓度，而远离阻挡层的籽晶层区域，即形成铜金属化层将电沉积其上的表面，具有低氮浓度或没有氮。可选地，籽晶层可包括三个不同氮含量的子层。则可认为能获得籽晶层对于阻挡层以及铜金属化层的充分粘着。
已知方法的缺点是不必要地复杂，尤其在需要控制氮气气氛以提供分级的籽晶层方面。
因此，本发明的第一目的是提供如上所限定的一种方法，在该方法中不需要控制氮气气氛，并且该方法仍可提供籽晶层对于阻挡层以及铜金属化层的充分粘着。
本发明的第二目的是提供在开始段落中限定的电子器件，其中在阻挡层和铜金属化之间有充分粘着。
第一目的的实现是由于在形成铜金属化之前加热籽晶层，以释放其氮含量而形成将籽晶层与衬底隔离的部分阻挡层。
第二目的的实现是由于在因氮通过界面的扩散而导致的界面处的区域中阻挡层是富集氮的。
加热籽晶层有利地促使了含氮铜分解，其有利地导致了降低薄层电阻连同所需的氮释放。释放的氮有效地对下面的衬底区域渗氮(nitridate)以提供用作阻挡铜籽晶层、以及随后淀积的铜金属化层扩散到衬底中的阻挡区域。在铜籽晶层已经在适当位置的原位下有效地获得了提高阻挡功效的优点。因此，在所需要以便提供有效的阻挡层的下面区域的渗氮之前已获得了铜籽晶层与半导体本体的需要的粘着。
在本发明的方法中，在涂敷铜金属化层之前加热籽晶层。如果在后面的阶段应用加热，则其不会有效。铜金属化层通常借助电镀来涂敷，并通过其后的化学机械抛光来进行抛光。如果在电镀后应用加热，则加热的施加将加热该铜金属化层。这将导致重新的结晶化，并可能导致铜金属化层中的破裂，如果在任意更后的阶段应用加热，则不能有效地进行氮的扩散。
还可能的是，通常在一个电子器件的制备中应用两次或更多次本发明的方法。在通过抛光除去多余的铜金属化后，铜金属化对加热步骤的灵敏度不会足够高而变得有缺陷。因此可能够提供第一铜金属化，包括加热步骤以实现氮的扩散，然后提供第二铜金属化，包括另一个加热步骤以实现第二铜金属化的籽晶层的氮扩散。
尽管优选在籽晶层淀积之后直接进行加热步骤以获得氮扩散到阻挡层中，但在其它方式中，如高压、催化剂的存在，同样可获得该扩散。
由于扩散以及随后的渗氮或下面衬底的氮富集，具有逐渐变化的氮含量的区域将出现在阻挡层和铜金属化之间的界面处。结果，在阻挡层和铜金属化之间的粘着将是充分的。由于氮从铜籽晶层向外的扩散，在籽晶层和铜金属化层之间的粘着也将是充分的。通过选择铜籽晶层的氮含量的选择可以最优化该粘着。
JP07090546公开了一种在衬底上具有铜金属化的半导体器件，其是通过使用含铜和含氮气体溅射靶而获得。这导致具有0.2-17％氮的含氮铜金属化。然而，其并未描述采取如本发明中的加热步骤来实现氮从铜金属化向外的扩散。结果，由于存在的铜金属化，铜金属化具有优秀的抗氧化能力却不具有减小的电阻。
在该方法的有利形式中，在铜籽晶层淀积之前淀积由释放的氮形成其部分的阻挡层。采用该形式，分立的阻挡层可由由任意适合的材料形成，特别是设置用于氮化的材料，或者可以已经包含了有利地可以富集的氮化物。优选地，阻挡层包括氮化钛或氮化钽。阻挡层可包括氮含量变化的几个子层。例如，有利的阻挡层为钽、氮化钽和钽的叠层，在加热步骤中对其最后一层渗氮。
含氮气氛可是任意的含氮气体，如对其可加入惰性气体的N2、N2H2、NH2、NH3、NO。优选地，含氮气氛是具有平均摩尔质量为20克每摩尔或更少的低重量气体。已经发现，通过使用这种低重量气体，含氮层的覆盖范围是充分的。这种气体的示例可包括，邻近氮源的Ne、He、H2、CH4。也可使用具有低氩含量的氩和氮的混合物，如80体积％的N2和20体积％的Ar的混合物。在本发明的进一步形式中，含氮气氛是包括作为氮源N2的气氛。已经发现，使用纯氮气体导致很好的效果。这种也可在另一含氮气氛中同样获得的好效果包括具有氮的15-25at％的氮含量，特别是约20at％的籽晶层的淀积。最优选是使用氮和氖的混合物。由于氖的低摩尔质量，衬底的覆盖范围是极好的。
在另一形式中，铜籽晶层包括至少两个子层，只有其中一个子层在含氮气氛中形成。这是有利的，因为其只需要铜籽晶层的部分或子层在氮气气氛中形成。也有利地提供用于随后结构以及处理步骤的灵活性。
以下通过参考附图的仅从示例性的方式详细描述本发明，其中：
图1A是描述在加热步骤前在硅上形成的含氮铜膜的RBS谱图；
图1B是描述在加热步骤后图1A的铜膜的RBS谱图；
图2是表示在硅上的铜层和含氮铜层的薄层电阻图表；
图3是描述在硅上的10nm钛上纯铜和含氮铜的薄层电阻图表，以及
图4表示本发明的电子器件的示例。
如所理解的，本发明的电子器件可以是半导体器件。然而，该电子器件同样可是电容器以及电感器的无源网络。本领域技术人员公知的可选器件，通常为包括衬底上的多个层的薄膜器件，同样也在本发明的范围内。本发明涉及的铜金属化工艺通常包括在半导体本体上阻挡膜的淀积以及随后的铜籽晶层的溅射淀积。在该实施例中，铜金属化层的电化学淀积跟随在铜籽晶层的淀积之后。
如任何技术人员可理解的，在该申请上下文中的术语“衬底”指在其上将淀积阻挡层和/或籽晶层的任意层或叠层。特别地，其包括其中限定多个半导体元件并可被一个或多个绝缘和互联层覆盖的半导体衬底。也可理解，衬底不需要具有平坦的表面。而是，在镶嵌或双镶嵌结构中其可以很好地成为在铜金属化淀积之后形成的非常适合的构图绝缘层。
然而，根据本发明，尽管气体混合物，例如，80％N2和20％Ar的混合物、或N2和He的混合物可提供适合的低重量工作气体，但是优选在纯氮的气氛中淀积至少部分铜籽晶层。在这种方式下，然后淀积在膜中具有约20％氮的含氮铜膜。然后该膜在例如150-300℃范围的温度下有利地分解；这导致电阻下降超过10倍，并且重要地是氮的释放。该氮的释放用作对下面的阻挡膜渗氮并因此阻挡铜扩散到半导体本体中。如WOA01/61847中公开的，该籽晶层可有利地用作在无源网络的硅衬底上的第一层。
因此，可理解本发明能有利地应用于任意能形成氮化物的合适的金属/合金膜、或可以被富集氮的现有氮化物膜。例如，这种膜包括钛或钽膜或氮化物如氮化钽。由此形成的阻挡铜扩散的特性对于其原位形成的简化以及已覆盖在铜籽晶层之上的存在尤其有利。
参考图1A和1B描述该整体方案。这些图为卢瑟福背散射谱图，其中归一化产额Y被给定作为以MeV的背散射能量E的函数。通过在层上提供具有2MeV能量的He束获得该谱。背散射的能量是层中原子的原子量的量度。归一化产额Y被限定作为每单位施加的He的返回He计数的数量，该数量很大程度决定于特定的原子。在图中通过实线表示试验结果，而用虚线表示模拟结果。
对于籽晶层，已获得图1A和1B。图1A表示在加热前通过在含氮气氛中溅射而获得的籽晶层的谱。图1B表示在加热发生后的籽晶层的谱。对比图1A和图1B观察，铜籽晶层中的氮数量明显地减少。分析该减少得出的结论是，在这种特定实施例中，在铜硅界面处将存在约20×1015Si3N4/cm2的数量。在图中还可看出，还存在一些碳和一些氧。认为氧来自一些铜的氧化成为CuO，以及认为碳存在于He束中。
图2表示对于在硅衬底上的150nm纯铜层以及30nm含氮铜层的试验结果。在该图中，将归一化的薄层电阻设置为在其中加热具有层的衬底的熔炉温度的函数。在试验开始时已设定薄层电阻为1，由于其容易地扩散到硅衬底中，因此该纯铜显示了急剧升高的薄层电阻。然而，含氮膜伴显示了与氮的释放相关的薄层电阻的降低。有利地，发现铜膜在硅上是稳定的直至熔炉温度在500℃的区域中，并且其有利地是由于作为铜扩散阻挡的硅的原位渗氮。结果，在冷却后薄层电阻保持较低。
图3是描述在硅上10nm的钛上对于纯铜层和含氮铜层的试验的图表。在该图表中，归一化薄层电阻绘制为熔炉温度的函数。由于铜和钛的扩散，铜的薄层电阻随着温度而增加，但含氮铜膜再次首先显示薄层电阻的降低，然后显示薄层电阻值的稳定直至550℃的温度。因此可以看出，氮的存在有利地用作阻挡铜-钛的相互扩散。
图4表示本发明的半导体器件的实施例。包括多个半导体元件，如场效应晶体管或双极晶体管的半导体衬底100覆盖以未示出的绝缘层。将该绝缘层光刻构图且随后将其蚀刻以限定沟槽。此后，使用化学气相淀积来淀积TaN的阻挡层121(为5nm Ta、15nm TaN以及5nm Ta的叠层)。其后淀积包括铜的200nm厚的籽晶层122。在N2气氛中通过溅射获得最初的15nm，接下来的185nm在Ar气氛中通过溅射获得。在30分钟期间加热到300℃后，通过电镀铜以及后来的化学机械抛光方式的抛光来生长铜金属化层101。然后淀积另一阻挡层114。随后，使用公知镶嵌技术提供另一铜金属化层102。在提供并构图绝缘层106、107后，通过硬掩膜108相互隔离，提供阻挡层123。其上溅射籽晶层124并加热籽晶层124以使氮扩散到阻挡层123，因此其富集氮。随后地，通过电镀生长铜金属化层102。
本发明提供一种在半导体本体上提供铜金属化的方法，包括在含氮的气氛中淀积铜以形成含氮铜籽晶层的步骤，以及在籽晶层上形成铜金属化，还包括加热籽晶层以释放氮而形成将籽晶层与半导体本体隔离的部分阻挡层的步骤。

Claims (10)

1、一种制造在衬底上具有铜金属化的电子器件的方法，该铜金属化包括籽晶层和铜金属化层，该方法包括步骤：
-在含氮的气氛中淀积铜以形成含氮的铜籽晶层；
-加热籽晶层以释放氮，从而形成将籽晶层与衬底隔离的部分阻挡层，以及随后
-在籽晶层上施加铜金属化。
2、根据权利要求1的方法，其中在铜籽晶层淀积之前淀积释放的氮形成其部分的阻挡层。
3、根据权利要求1或2的方法，其中加热籽晶层到超过150℃的温度。
4、根据权利要求3的方法，其中将籽晶层加热至300℃-500℃范围内的温度。
5、根据在前任一权利要求的方法，其中含氮气氛是包括N2作为氮源的气氛。
6、根据在前任一权利要求的方法，其中铜籽晶层包括至少两个子层，其中只有一层在含氮气氛中形成。
7、根据在前任一权利要求的方法，其中氮化物阻挡层包括氮化钛或氮化钽。
8、根据在前任一权利要求的方法，其中阻挡层由将形成氮化物的任意合适金属形成，或由可以通过从含氮铜层中氮的释放而富集的氮化物材料形成。
9、一种具有在其上存在有包括金属氮化物的阻挡层和铜金属化的叠层的衬底的电子器件，该阻挡层和该铜金属化具有共同的界面，特征在于由于氮通过界面的扩散，阻挡层在界面处的一个区域中富集氮。
10、根据权利要求9的电子器件，特征在于其可以从具有临近于界面的铜籽晶层的铜金属化获得，在扩散前该铜籽晶含有15-25原子％的氮。
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