CN112899735A - 电化学电镀方法 - Google Patents

电化学电镀方法 Download PDF

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CN112899735A
CN112899735A CN202110150776.1A CN202110150776A CN112899735A CN 112899735 A CN112899735 A CN 112899735A CN 202110150776 A CN202110150776 A CN 202110150776A CN 112899735 A CN112899735 A CN 112899735A
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cobalt
substrate
seed layer
nickel
bath
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约翰·W·莱姆
伊斯梅尔·埃迈什
罗伊·沙维夫
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Applied Materials Inc
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Abstract

用于将导电膜施加至具有种晶层的基板上的电化学工艺包含把基板放入以与含钴或镍的电化学电镀浴接触，且电镀浴的pH为4.0至9.0。引导电流通过浴而至基板。浴中的钴或镍离子沉积至种晶层上。电镀浴可含氯化钴和甘氨酸。电流可为1‑50毫安/平方厘米的范围。完成电化学工艺后，可以将基板移出电镀浴、清洗并干燥，接着以200℃至400℃的温度退火，以改善材料性质及减少接缝线缺陷。可通过多次循环来执行电镀及退火工艺。

Description

电化学电镀方法
本申请是申请日为2015年3月16日、申请号为201580013199.4、名称为“电化学电镀方法”的发明专利申请的分案申请。
技术领域
本发明的领域为用于电化学处理微型工件、晶片或基板的方法。
背景技术
诸如微型的电子装置、机电装置或光学装置之类微电子装置通常是在工件或基板上和/或工件或基板内制造，例如硅晶片。在典型制造工艺中，例如在半导体材料晶片上，首先利用化学气相沉积(CVD)、物理气相沉积(PVD)、无电电镀(electro less plating)工艺或其它合适的方法将导电种晶层施加至基板的表面上。形成种晶层后，在存在含金属离子的电处理溶液的情况下，通过于种晶层与一或多个电极间施加合适的电势，将金属覆盖(blanket)层或经图案化的金属层电镀至基板上。接着在后续工序中清洁、蚀刻和/或退火处理基板，以形成装置、触点或导线。一些基板可具有阻挡层，种晶层形成于阻挡层上。
目前，微电子装置大多制作在镀铜基板上。尽管铜具有高的导电率，但铜通常需要阻挡层，例如氮化钽(TaN)，以防止铜扩散到基板或基板上的介电材料内。此类阻挡层具有相对低的导电率。利用已知技术，以使用酸铜化学品或电镀溶液电镀的铜，对基板上的特征结构进行填充。这些化学品经常使用添加剂以促进超共形(super conformal)填充工艺(特征结构填充主要是从下往上，而不是从侧边往内)及形成无空隙(void-free)填充。随着特征结构尺寸缩小，以传统铜电镀工艺实现无空隙填充变得更加困难。又随着特征结构变得更小，由于必须维持最小的阻挡层厚度以防止铜扩散，所以无论特征结构尺寸如何，铜所需的阻挡层仍占很大体积。
例如，若防止铜扩散所需的最小阻挡层厚度为3nm，则对于临界尺寸(criticaldimension)60nm且深宽比(aspect ratio)4：1的特征结构而言，阻挡层大致占横断面积的11％。然而，对于临界尺寸20nm且深宽比2：1的特征结构来说，阻挡层厚度必须保持为3nm，但如此便占横断面积的33％。在此情况下，(具有低导电率的)阻挡层的体积按比例更大，因此互连、通孔(via)或其它特征结构的电阻按比例也更高。随着特征结构日益缩小，铜与阻挡层的比例增加到电阻变得无法接受的程度。
用于克服此技术挑战而提出的一种方法是用不需要阻挡层的金属取代铜，例如钴。尽管钴的电阻比铜高(钴为6微欧姆-厘米；铜为2微欧姆-厘米)，但钴不需要阻挡层，因为钴不会扩散到硅或电介质内。利用化学气相沉积(CVD)将钴施加至基板上，此方法通常可成功用于更小特征结构，例如7-10nm的特征结构。但是CVD不太适于填充大于约10nm的特征结构。因此，仍需改良技术。
附图简单说明
图1A是具有TaN阻挡层和Cu种晶层的基板上的未填充或未电镀结构的扫描式电子显微镜(SEM)图像。在一些应用中，阻挡层可以是其它材料，例如TiN，或者可以没有阻挡层。种晶层也可以是CVD钴。
图1B示出图1A现已填充由碱性电镀浴电化学沉积的钴的结构。
图2A是于TaN/Co种晶层上的电镀有钴的类似结构的SEM图像，采用pH6.5的钴-甘氨酸电镀浴电镀，且示出了接缝线缺陷。
图2B示出图2A退火处理后的结构，且示出了最小化或者消除的接缝线。
图3是于CVD Co种晶层上的电镀有钴的另一种结构的SEM图像，采用pH 8.5的钴-EDA电镀浴电镀。
图4A至图4E是本发明的方法的实施方式示意图。
图5是退火后的线电阻的测试数据的曲线图。
图6A至图6C是超共形填充的示意图。
图7A至图7C是共形填充的示意图。
图8A至图8C是共形填充、然后退火处理的示意图。
具体实施方式
已提出各种使用酸性与碱性钴浴的已知钴电镀方法。然而，将钴电镀至具有很小特征结构(例如60纳米(nm)、40nm、30nm或更小的特征结构)的基板上会面临不同的挑战。具有很小特征结构的基板必然具有很薄的种晶层。对这些基板使用已知的钴电镀方法通常会使很薄的种晶层溶解，以致妨碍适当电镀。本发明的方法采用具有特定pH范围的钴浴，以最小化种晶层的腐蚀。
镍的电镀特性与钴相似。还可将所述钴的用法应用于取代钴的镍。在此提及的互连包括基板上或基板内所用的其它特征结构，例如沟槽、孔和通孔。
通过导电基板上的电化学沉积可实现亚微米互连内部的金属沉积。电镀的金属可选自包括铜、钴、镍、金、银或铂的清单。共形及超共形电化学沉积金属后可进行可选择的热处理。
中性至碱性水溶液可用于电化学电镀金属的沉积。例如，钴或镍复合电镀液可用于电化学沉积钴或镍至亚微米互连内或基板上的其它特征结构内。可以为基板提供种晶层，种晶层可由无电沉积、物理气相沉积或化学气相沉积形成。种晶层中所用的材料可包括铜、锰掺杂铜、钌(Ru)和其它材料。硅化钴或硅化镍也可用在种晶层中。若有的话，基板上的阻挡层可由化学气相沉积(CVD)或其它的已知技术施加。
电镀或电化学沉积工艺后可执行退火步骤，以改善电化学电镀的钴或镍的材料性质，及减少共形电镀相关的接缝线空隙。在本发明的方法中，电镀后退火可以于低于传统的铜工艺所用的温度进行。退火步骤能稳定电镀的膜。退火步骤也有助于移除来自共形电镀工艺的接缝线和微空隙。退火步骤还可以通过驱除因电镀条件而可能被俘获的杂质来改善膜的性质。对于一些应用，可依据具体电镀条件与化学品而省略退火步骤。例如，促进超共形生长及引入少量杂质的钴电镀方案可不需退火步骤。
A.使用钴的电化学沉积
i.综述
本发明的方法图解于图4A至图4E中。在图4A中，基板10(例如硅晶片)具有特征结构12和导电种晶层14。在一些应用中，可在种晶层14下面设置阻挡层(未图示)。在图4B中，钴或镍共形或超共形膜16被电镀至种晶层14上。膜16可部分地或完全地填充特征结构，如图4B所示，膜16部分地填充特征结构12。膜16的厚度足以提供特征结构的至少10％、20％、30％、40％或50％填充(对照于实质上无显著填充的种晶层14)。阻挡层可选地为PVD TaN、ALD TaN、PVD TiN、ALD TiN、ALD MnN、CVD MnN、CVD NiSi或CoSi，其中PVD是物理气相沉积，CVD是化学气相沉积，ALD是原子层沉积。
图4C示出退火使膜16回流(reflow)以进一步填充特征结构12。图4D示出覆盖(capping)层或金属层18的沉积，该层可为相同金属(如同用于膜16的钴或镍)或不同金属。图4E示出化学机械抛光后的基板，且覆盖层18选择性地被移除而留下填满的特征结构12。
可使用pH 4至pH 9范围的中性至碱性钴电镀溶液，将膜16电镀至种晶层14上。电镀溶液可含螯合剂，例如柠檬酸盐、甘氨酸、酒石酸盐、乙二胺等。
图6A至图6C图示超共形填充基板上的特征结构，例如沟槽或通孔。如图所示，特征结构主要从下往上填充、而不是从侧边往内填充，以提供无缝电镀的特征结构。填充也可以以电镀共形膜、然后执行退火步骤或形成另一层超共形膜来进行。图7A至图7C示出共形填充，其中特征结构主要从侧边往内填充，且于所填充的特征结构中形成接缝。图8A至图8C示出与图7A至图7C一样的工艺，但是在退火后图8A至图8C具有无缝填充的特征结构。共形或超共形电镀可用于实施所述方法。
ii.工艺详述
1.为基板提供诸如CVD钴或无电沉积钴之类的导电种晶层，然而该导电层也可使用其它材料，诸如铜、镍、金、银、钯和/或钌。图1A示出未填充的特征结构的实例，未填充特征结构具有施加于基板上的阻挡层(例如TaN)，及该阻挡层上的铜种晶层。图2A示出在具有于TaN阻挡层上的CVD钴层的基板上共形电化学沉积(ECD)钴，且具有明显的接缝线缺陷。图3示出CVD钴种晶层上共形ECD钴的实例。
2.可以使用预镀(pre-plating)处理，即，在电镀前，将还原剂(例如He/H2、合成气体(forming gas)等)施加于基板。可在弱酸性、中性或碱性电镀浴中，使结构电镀上钴。在图1B、图2A及图2B的实例中，氯化钴与甘氨酸浴在pH6.5下用于钴沉积。在图3中，氯化钴与EDA浴在pH 8.5下用于钴沉积。用于电化学沉积工艺的电流密度可为1-50毫安/平方厘米的范围。
3.若种晶层更易受腐蚀影响，例如CVD钴种晶层，则可使用中性至碱性电镀浴。当pH从6.5提高到8.3时，一般可以获得由化学气相沉积施加的钴种晶层上的完全覆盖电化学沉积钴。电镀浴的pH或可为下列范围之一：7.5至8.5；7.8至8.5；8.0至8.5；或7.8至9.0。
4.完成共形或超共形电化学沉积钴后，可以在200℃至450℃的温度热处理基板，以改善材料性质和/或减少接缝线缺陷。图2B示出以350℃在H2/He环境中退火后的基板。扫描式电子显微镜图像中已看不到接缝线。或者可使用其它气体，例如N2/He或纯H2。如图2B所示，退火工艺后，也改善了表面粗糙度。
利用缓慢电镀工艺填充特征结构、接着退火处理以改善材料性质、然后沉积覆盖层18供化学机械抛光，可以执行多重电镀多重退火工艺。电镀钴可用于覆盖层18。在具有第一电镀和第二电镀步骤的多重电镀工艺中，第一和第二电镀步骤提供第一膜和第二膜于基板上，例如以200℃至450℃的温度退火处理基板后，可以执行第三电镀步骤，以提供金属层于第二膜上。接着可以化学机械抛光金属层。
iii.测试结果
利用所述方法填充60nm-25nm范围的特征结构。测试结果显示成功电镀至具有高的薄层电阻(sheet resistance)的薄种晶层，即300毫米(mm)晶片上的200欧姆/sq的种晶层上。此类种晶层通常会在传统的酸铜电镀溶液中快速腐蚀，但使用上述钴或镍电镀溶液时没有受到明显蚀刻或腐蚀。测试结果也证实：使用弱酸性至碱性钴电镀溶液，成功电镀钴膜至6nm CVD钴种晶层上。
如图5所示，测试数据也显示，电镀后退火处理降低了线电阻和覆盖膜电阻。对具有CVD钴种晶层的基板也可以实施多重电镀多重退火工艺。多重电镀工艺的一个实例为利用缓慢电镀溶液填充特征结构，接着于化学机械抛光之前把基板移到另一腔室，用于快速电镀覆盖或金属层18。
B.使用镍的电化学沉积
上述方法和参数也可配合镍使用。
相较于仅有CVD的工艺，上述方法保证产量高得多并可降低成本，故适于大量制造。
C.附加方法
通过把基板放入以与包含金属的电化学电镀浴接触、且该金属选自钴或镍、电镀浴的pH为4.0至9.0，可以实施沉积导电膜至基板上的亚微米互连内的电化学工艺，该基板上具有种晶层。按1-50毫安/平方厘米的比率引导电流通过浴而到达基板，以沉积金属膜至基板的特征结构上。将基板移出电镀浴、清洗和干燥，接着可选地进行退火，例如以200℃至450℃的温度退火，以促使金属膜回流并进一步填充基板的特征结构。电镀浴可包括氯化钴和/或甘氨酸。这些步骤可反复进行，且其间可有或没有退火步骤。例如，晶片可经历电镀、干燥及退火处理的至少两次循环。
另一个工艺通过把基板放入以与含钴或镍盐的电化学电镀浴接触、且电镀浴的pH为4.0至9.5，可用于将导电膜施加至基板上，基板具有种晶层、第一尺寸的第一特征结构和第二尺寸的第二特征结构，该第二尺寸大于第一尺寸。引导电流通过浴来执行第一电镀步骤，以减少电镀浴中的钴或镍离子，和沉积共形或超共形的第一钴或镍膜至种晶层上，第一钴或镍膜完全填充第一特征结构，但不完全填充第二特征结构。接着，引导电流通过浴来执行第二电镀步骤，以减少电镀浴中的钴或镍离子，及沉积共形或超共形的第二钴或镍膜至第一钴或镍膜上，第二钴或镍膜完全填充第二特征结构。

Claims (12)

1.一种电化学方法，用于将导电膜施加至具有种晶层的基板上，所述方法包含以下步骤：
把所述基板放入以与含钴或镍盐的电化学电镀浴接触，且所述电镀浴的pH为6.5至8.5；及
引导电流通过所述浴，以减少所述电镀浴中的钴或镍离子，和沉积钴的超共形膜或镍的超共形膜至所述种晶层上，
其中所述种晶层包含所述基板上的铜、钴、金、银、钯和/或钌。
2.如权利要求1所述的方法，所述电镀浴包含氯化钴或其它钴盐。
3.如权利要求1所述的方法，所述电镀浴包含甘氨酸或其它螯合剂。
4.如权利要求1所述的方法，所述电流为1-50毫安/平方厘米的范围。
5.如权利要求1所述的方法，进一步包含以200℃至450℃的温度退火处理所述基板。
6.如权利要求5所述的方法，所述退火处理将引起所述膜回流而完全填充所述基板上的多个特征结构。
7.如权利要求5所述的方法，其中所述退火处理是在氢、氦、氮、还原气体或氨的环境中进行。
8.如权利要求1所述的方法，其中所述电镀浴的pH为7.5至8.5。
9.如权利要求1所述的方法，所述电镀浴进一步包含螯合剂，所述螯合剂与钴金属离子复合。
10.如权利要求1所述的方法，其中所述钴或镍沉积至所述基板上的亚微米互连内。
11.如权利要求1所述的方法，所述基板无阻挡层。
12.如权利要求5所述的方法，所述退火处理将引起所述超共形膜回流而完全填充所述基板上的亚微米互连，所述亚微米互连在所述退火处理步骤后无接缝线缺陷。
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US20150357195A1 (en) 2015-12-10
CN110233099A (zh) 2019-09-13
KR20170005513A (ko) 2017-01-13
KR101820002B1 (ko) 2018-01-18
TW201802296A (zh) 2018-01-16
US9496145B2 (en) 2016-11-15
US20150270133A1 (en) 2015-09-24
CN106104757A (zh) 2016-11-09
CN110233099B (zh) 2023-05-16
WO2015142745A1 (en) 2015-09-24
TWI609996B (zh) 2018-01-01
US9704717B2 (en) 2017-07-11
EP3120378A4 (en) 2017-12-06
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EP3120378A1 (en) 2017-01-25
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