CN110024132A - 选择性沉积无腐蚀金属触点的方法 - Google Patents

选择性沉积无腐蚀金属触点的方法 Download PDF

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CN110024132A
CN110024132A CN201780071771.1A CN201780071771A CN110024132A CN 110024132 A CN110024132 A CN 110024132A CN 201780071771 A CN201780071771 A CN 201780071771A CN 110024132 A CN110024132 A CN 110024132A
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cobalt
substrate
protective layer
forming
plasma
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徐翼
马飞跃
雷雨
大东和也
维卡什·班西埃
吴凯
詹·跃·王
常梅
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Applied Materials Inc
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Abstract

形成触点线的方法包括清洁在沟槽中的钴膜的表面及在此钴的表面上形成保护层，此保护层包括硅化物或锗化物中的一或多种。也公开了具有触点线的半导体装置。

Description

选择性沉积无腐蚀金属触点的方法
技术领域
本发明一般地涉及沉积方法与金属触点。尤其是，本发明涉及沉积实质上无腐蚀的钴触点的工艺。
背景技术
随着FINFET朝向更小节点(<10nm)发展，由于钴的低线路电阻与在<20nm的窄沟槽处的无孔隙间隙填充能力，钴取代传统的钨作为金属触点与局部互连件。
然而，在接着介电堆叠的干式蚀刻以打开触点孔(通孔)与光刻胶灰化后的湿式清洁之后，创造出在包括显著的下切(undercut)与凹部的钴沟槽内的严重Co腐蚀。下切与凹部两者对于达成用于接下来的金属触点形成的良好间隙是极大的阻碍，且致使非常高的触点电阻及装置可靠性问题。
Co腐蚀的一个主要原因是：钴会与湿式化学溶液反应，并且钴由于相较于水中氧的还原性的低电位而被溶解成离子的形式：
Co2+(aq)→Co(-0.28V) (I)
O2+2H2O+4e-→4OH-(+0.4V) (II)
此外，若有诸如钨的不同金属，其可作为阴极，于是电镀(galvanic)腐蚀发生。电镀腐蚀甚至可在没有第二金属下发生且致使在产物结构中的遗失钴。
再者，在Co沟槽上方的间隙填充期间，沿着侧壁会有着某些孔隙或接缝或弱附着。在接下来的化学机械平坦化(CMP)步骤期间，这些孔隙或接缝或弱附着被暴露于CMP腐蚀化学品(诸如H2O2)且会使得此化学品向下渗透以侵蚀Co并致使遗失钴和因此断开电路。
因此，需要一种抵抗水分与湿式化学品的攻击的层。对于钨触点，钨本身抵抗水分攻击及某些湿式化学品攻击(取决于特定化学品与pH值)。
发明内容
本公开内容的一或多个实施方式关于形成触点线的方法。提供具有沟槽的基板表面，且沟槽中具有钴。钴的表面被清洁而保护层形成在此表面上。保护层包含硅化物或锗化物中的一或多种。
本公开内容的额外实施方式关于形成触点线的方法。此方法包含提供在介电阻挡(block)中具有钴沟槽的基板表面。通过以下的一或多个步骤来清洁钴的表面：在H2中烘烤基板、将基板暴露于H2等离子体或以大于约0.5原子百分比的含量的可选的额外元素在氩等离子体中溅射此钴表面。保护层形成在钴的表面上。保护层包含硅化物或锗化物中的一或多种。形成此保护层包含将钴浸泡在以下的一或多种物质中：硅烷、二硅烷、三硅烷、四硅烷、更高级的硅烷、没有氟原子的硅基卤化物(silyl halide)、锗烷、二锗烷、三锗烷、四锗烷、更高级的锗烷或没有氟原子的锗卤化物，此浸泡步骤发生在范围为约200℃至约600℃的温度，其中在没有等离子体下形成硅化物。通过将此基板暴露于在范围为约300℃至约600℃的温度的退火环境，来退火此具有保护层的基板。此退火环境包含Ar、N2、Ar/H2、N2/H2、H2、He或NH3。在基板上沉积钴膜于保护层上方。通过CVD或PVD中的一或多种来沉积此钴膜，且可选的退火步骤以回流(reflow)此钴膜。
本公开内容的进一步实施方式关于半导体装置触点线，包括具有带沟槽的表面的基板，沟槽具有底部与侧壁。介电层在沟槽的侧壁上。钴间隙填充材料是在沟槽之内的侧壁之间。钴间隙填充材料被介电层所约束。保护层在此钴层上。保护层包含硅化物或锗化物中的一或多种。钨衬垫在保护层的顶部上而钨金属在钨衬垫的顶部上。
附图说明
以上简要概述本发明的详述特征可以被详细理解的方式、以及本公开内容的实施方式的更特定描述，可通过参照实施方式来理解，一些实施方式绘示于所附图式中。然而，应注意，随附图式仅绘示本发明的典型实施方式，因而不应视为对本发明的范围的限制，因为本发明可允许其他等同有效的实施方式。
图1示出根据本公开内容的一或多个实施方式的半导体装置的截面示意图；
图2示出根据本公开内容的一或多个实施方式的半导体装置的截面示意图；及
图3示出根据本公开内容的一或多个实施方式的半导体装置的截面示意图。
在随附图式中，类似部件和/或特征会具有相同的附图标号。此外，相同类型的各种部件可通过接着附图标号的破折号与区别类似部件的第二标号而被区别。若只有第一附图标号被使用在本说明书中，此描述可应用于具有相同第一附图标号的类似部件的任一个，而与第二附图标号无关。
具体实施方式
在描述本发明的数个示例性实施方式之前，将理解到本发明并不局限在接下来的说明书中所阐述的处理步骤或构造的细节。本发明可为其他实施方式且可以各种方式实施或执行。
当本文使用“基板”时，其意指在制造处理期间于其上执行膜处理的任何基板或形成在基板上的材料表面。例如，在其上可执行处理的基板表面包括以下材料，视应用而定，诸如硅、氧化硅、应变硅、绝缘体上硅(SOI)、碳掺杂氧化硅、非晶硅、掺杂硅、锗、砷化镓、玻璃、蓝宝石、以及诸如金属、金属氮化物、金属合金和其他导电材料的任何其他材料。基板包括(无限制于)半导体晶片。基板可暴露于预处理工艺以抛光、蚀刻、还原、氧化、羟基化(hydroxylate)、退火、UV固化、电子束固化和/或烘烤基板表面。除了直接在基板本身的表面上的膜处理之外，所公开的任何膜处理步骤也可在如之后更详细公开的形成在基板上的下层上执行，而术语“基板表面”意欲包括如上下文所指示的此下层。因此例如，在膜/层或部分的膜/层已经沉积在基板表面之上，此新沉积的膜/层的暴露表面变成此基板表面。
本公开内容的实施方式有利地提供在钴的顶部上选择性形成导电保护层的方法。某些实施方式有利地提供正好在钴CMP之后或在钴的顶部上的通孔或沟槽的开启之后可执行的方法。某些实施方式有利地提供使用与包括硅烷(诸如SiH4、SiH2Cl2、Si2H6)与锗烷(诸如GeH4、GeH2Cl2)的气体整合的处理腔室的方法。此层可由硅或锗或甚至任何其他的膜所构成，此膜可选择性生长在钴上且成为导电层，通过诸如等离子体处理、热退火、UV烘烤之类的的后处理。某些实施方式有利地由热处理形成导电层，即没有等离子体暴露。
在形成之后，保护层，例如，可为金属(例如钴)的硅化物或锗化物。在某些实施方式中，形成保护层之后进行的是用于接下来的通孔或沟槽间隙填充的衬垫的沉积，此沉积可在整合系统中。选择性沉积可在整合系统中完成而不破坏真空。
在某些实施方式中，此方法包含在H2环境中于250-500摄氏度烘烤基板，以减少来自先前处理的钴氧化物或卤化物。将此基板浸泡在硅烷或锗烷中于约250-500摄氏度持续一特定时间量。可选地，可接着使此基板退火(例如基于热预算、电阻和/或回流状态)。
在某些实施方式中，此方法包含将基板暴露于H2(可与其他惰性气体混合)等离子体于>200摄氏度，以减少在金属(例如钴)表面上的氧化物、卤化物及碳污染。此基板浸泡在硅烷或锗烷中于约250-500摄氏度持续一特定时间量。可接着进行可选的退火(例如基于热预算、电阻及/或回流状态)。
在某些实施方式中，以氩等离子体或H2等离子体或Ar/H2混合物等离子体溅射此基板，以清洁金属(例如钴)顶表面。可接着将此基板浸泡在硅烷或锗烷中于约250-500摄氏度持续一特定时间量。可接着进行可选的退火(例如基于热预算、电阻及/或回流状态)。
为了在下方金属(例如钴)与顶部硅化物或锗化物之间形成良好欧姆接触(ohmiccontact)，某些实施方式具有在接下来的硅化或锗化之前的整合预清洁(诸如H2烘烤、H2等离子体、Ar等离子体、Ar与H2等离子体)。
在某些实施方式中，此方法有利地提供在顶部处的抗腐蚀的钴硅化物或锗化物，使得在顶部通孔或沟槽开启期间的钴下切与凹部会被显著地减少。此也造成接下来的通孔或沟槽间隙填充的显著改善，及较低的接触电阻。在某些实施方式中，此方法有利地提供抗腐蚀钴硅化物或锗化物，其也可阻挡CMP湿式化学品的向下渗透路径并避免钴腐蚀。在一或多个实施方式中，此方法有利地提供硅烷或锗烷浸泡，其也可调制通孔或沟槽侧壁状态，并改善接下来的间隙填充并进一步最小化湿式化学腐蚀。
参照图1与2，一或多个实施方式关于形成半导体装置100的方法。提供具有沟槽110的基板105，沟槽110以钴130填充。钴130具有表面135，表面135被暴露以用于进一步处理。
可选的介电衬垫120可形成在基板105或沟槽110之上。介电衬垫120可为任何合适介电材料，所述介电材料包括但不限于钛或硅的氮化物、氧化物或碳化物。介电衬垫120可共形地或非共形地形成在基板105与沟槽110之上。
钴130可通过任何合适工艺来沉积，所述工艺包括但不限于化学气相沉积(CVD)、原子层沉积(ALD)或物理气相沉积(PVD)。在某些实施方式中，由CVD沉积钴130膜(也被称为层或间隙填充材料)。在某些实施方式中，由ALD沉积钴130膜。
清洁钴130的表面135，以从表面135移除污染物(例如氧化物、卤化物或碳化物)。在某些实施方式中，通过在氢气环境中烘烤基板以清洁表面135。在某些实施方式中，此氢气环境是没有等离子体暴露的热环境。在一或多个实施方式中，此氢气环境持续全部清洁时间中的至少一部分包含等离子体。
在某些实施方式中，通过溅射清洁表面135。表面135暴露至等离子体，此等离子体从钴130层的表面135溅射材料。此溅射等离子体可包括氩、氦、氖或氪的一或多者。在某些实施方式中，此溅射等离子体实质上仅包含氩。当以此方式使用，“实质上仅”意味着此等离子体气体是大于99.5原子百分比的所述物质。在某些实施方式中，此等离子体气体包含于原子基准上浓度为大于或等于约90％、95％、98％或99％的氩。
在某些实施方式中，此溅射等离子体包括额外的元素以调节表面溅射的量。此额外元素的量大于或等于约0.5原子百分比。在某些实施方式中，此溅射等离子体包括于原子基准上含量为大于或等于约1％、2％、3％、4％、5％、10％、15％或20％的额外元素。此额外元素可为任何合适元素，所述元素包括但不限于硼、砷、磷、锂、钠或氢。
在清洁表面135之后，保护层140形成在钴130的表面135之上，如图2所示。某些实施方式的保护层140包含硅化物或锗化物中的一或多种。
在某些实施方式中，形成保护层140包含形成钴硅化物层。可通过将钴130浸泡在含硅化合物中，来形成此钴硅化物。某些实施方式的含硅化合物包含硅烷、二硅烷、三硅烷、四硅烷、更高级的硅烷或硅基卤化物中的一或多种。在某些实施方式中，此含硅化合物是实质上没有氟原子的硅基卤化物。在所使用的这一方面，“实质上没有氟原子”意味着在所有的卤素原子的基础上有小于5、4、3、2或1原子百分比的氟原子。
在某些实施方式中，形成保护层140包含将钴130浸泡在含锗化合物中。某些实施方式的含锗化合物包含锗烷、二锗烷、三锗烷、四锗烷、更高级的锗烷或锗卤化物中的一或多种。在某些实施方式中，含锗化合物是实质上没有氟原子的锗卤化物。
形成保护层140可发生在任何合适温度。在某些实施方式中，保护层140形成在范围为约200℃至约600℃的温度，或在范围为约300℃至约500℃的温度，或约400℃。
可在具有或没有等离子体暴露的浸泡期间形成保护层140。在某些实施方式中，没有等离子体的条件下形成保护层140，而在钴上形成分离的硅化物或锗化物层。在一或多个实施方式中，此保护层是分离的且与钴层以限定的界面或非常小的界面区而分隔。某些实施方式的钴130与保护层140不是同质的，或者从钴的底部至钴的顶部不是固定的梯度。保护层140的厚度可在为约1nm至约50nm的范围中、或在约2nm至约40nm的范围中、或在约3nm至约30nm的范围中。
某些实施方式的保护层140形成在范围为约0.5托至约100托的压力、或范围为约1托至约50托的压力、或范围为约5托至约25托的压力。在某些实施方式中，通过将钴130浸泡持续在范围为约1秒至约300秒的时间而形成保护层140。
在某些实施方式中，保护层140在形成之后被退火。可通过任何合适工艺在任何合适温度完成退火。合适工艺包括但不限于等离子体退火、尖峰退火(spike anneal)、快速热退火、等离子体退火及热退火。在某些实施方式中，退火包含将基板暴露于范围为约300℃至约600℃的温度的退火环境。在某些实施方式中，退火环境包含Ar、N2、Ar/H2、N2/H2、H2、He或NH3。某些实施方式的退火压力在约100毫托至约300托的范围中、在约1托至约200托的范围中、或在约10托至约100托的范围中。
在形成保护层140之后，在基板105之上沉积金属膜150(如图2所示)于保护层140上方。某些实施方式的金属膜150包含钴。某些实施方式的金属膜150主要由钴所组成。在所使用的这一方面，“主要由钴所组成”意味着此金属膜150是大于或等于约99原子百分比的钴。可通过任何合适工艺形成金属膜150，所述工艺包括但不限于CVD、ALD或PVD。在某些实施方式中，金属膜150被退火以回流此膜以形成更同质的膜。
在某些实施方式中，在没有空气断路(air break)的情况下执行以下步骤：清洁钴膜130、形成保护层140及退火保护层140。此可通过使用整合或群集系统而完成，其中基板在受控真空环境中于腔室之间移动。
参照图3，本公开内容的某些实施方式关于半导体装置200。在某些实施方式中，半导体装置200包含触点线。提供具有表面205的基板205，表面205具有形成于其中的沟槽210。沟槽210可为类似于图2所示的沟槽，或可为通孔或不规则外形的沟槽，类似于图3所示。
介电层220形成在沟槽210的侧壁上。图3所示的介电层220也可称为介电阻挡。钴230间隙填充材料在沟槽210之内的侧壁之间。钴230间隙填充材料可由在钴230间隙填充材料与介电层220之间的可选的金属氮化物层所约束。
保护层240形成在钴230间隙填充材料之上，使得钴230间隙填充材料的顶部被保护层240所覆盖。在某些实施方式中，保护层240包含硅化物或锗化物中的一或多种。
在某些实施方式中，金属膜250形成在介电层220与钴230间隙填充材料的顶部之上。金属膜250可为任何合适金属，所述金属包括但不限于钨或钴。在某些实施方式中，钨衬垫在保护层的顶部上，如金属膜250。在某些实施方式中，钨衬垫是形成在介电层与保护层之上的相对薄的层，且具有较厚的块体沉积钨或钴金属形成在钨衬垫之上。在某些实施方式中，钴衬垫是在保护层的顶部之上，如金属膜。在某些实施方式中，钴衬垫是形成在介电层与保护层之上的相对薄的层，且具有较厚的块体沉积钨或钴金属层在钴衬垫之上。
根据一或多个实施方式，在形成此层之前和/或在形成此层之后，此基板经受处理。此处理可在相同腔室或在一或多个分开的处理腔室中执行。在某些实施方式中，此基板从第一腔室移动至分开的第二腔室用以进一步处理。此基板可直接地从第一腔室移动至分开的处理腔室、或可从第一腔室移动至一或多个移送腔室，然后移动至分开的处理腔室。因此，此处理设备可包含与移送站连通的多个腔室。此种设备可称为“群集工具”或“群集系统”，及类似物件。
通常，群集工具是包含多个腔室的模块系统，其执行各种功能，所述功能包括基板中心找寻及定位、除气、退火、沉积和/或蚀刻。根据一或多个实施方式，群集工具包括至少一第一腔室与中央移送腔室。中央移送腔室可容纳可在处理腔室与装载锁定腔室之间与之中运送基板的机器人。移送腔室通常维持在真空状态且提供用于从腔室运送基板至另一腔室和/或位在群集工具的前端处的装载锁定腔室的中间阶段。本发明可采用的两种广为人知的群集工具是及两者可购自加州圣克拉拉的应用材料公司。然而，由于执行如本文所述的处理的特定步骤，可改变腔室的确切布置与组合。可使用的其他处理腔室包括但不限于循环层沉积(cyclical layer deposition,CLD)、原子层沉积(ALD)、化学气相沉积(CVD)、物理气相沉积(PVD)、蚀刻、预清洁、化学清洁、诸如RTP的热处理、等离子体氮化、除气、定位、羟基化及其他基板处理。通过在群集工具上的腔室中执行处理，在沉积后续膜之前，由于大气杂质的基板的表面污染可被避免且没有氧化现象。
根据一或多个实施方式，此基板连续地处在真空或“装载锁定”状态下，且当从一腔室移动至下一个腔室时，不暴露于周围空气。移送腔室因此处在真空下且被“抽吸(pumped down)”至真空压力下。惰性气体可存在于处理腔室或移送腔室中。在某些实施方式中，惰性气体用于作为净化气体以移除某些或所有的反应物。根据一或多个实施方式，在沉积腔室的出口处注入净化气体以避免反应物从沉积腔室移动至移送腔室和/或额外的处理腔室。因此，惰性气体的流动在腔室的出口处形成帘幕。
此基板可在单一基板沉积腔室中处理，其中在处理另一基板之前，装载、处理及卸载单一基板。也可以连续方式处理此基板，类似于输送系统，其中多个基板被单独地装载在腔室的第一部分中，移动穿过腔室且从腔室的第二部分卸载。腔室与相关的输送系统的外形可形成直线路径或弯曲路径。此外，处理腔室可为旋转料架(carousel)，其中多个基板移动围绕中心轴且在整个旋转料架路径中暴露于沉积、蚀刻、退火、清洁、类似工艺。
在处理期间，基板可被加热或冷却。此加热或冷却可通过任何合适方式完成，所述方式包括但不限于改变基板支撑件的温度与使加热或冷却的气体流动至基板表面。在某些实施方式中，基板支撑件包括加热器/冷却器，所述加热器/冷却器可被控制以传导地改变基板温度。在一或多个实施方式中，被应用的气体(反应性气体或惰性气体)被加热或冷却以局部地改变基板温度。在某些实施方式中，加热器/冷却器位在腔室内邻近于基板表面以对流地改变基板温度。
此基板在处理期间也可为固定的或旋转的。旋转的基板可被连续地旋转或以分离(discreet)步骤方式旋转。例如，基板可在整个处理过程中被旋转，或基板可在暴露于不同的反应性气体或净化气体之间被小量地旋转。在处理期间旋转基板(连续地或步进地)可助于产生更均匀的沉积或蚀刻，通过最小化例如在气体流动几何模型中的局部变化的效应。
整个本说明书中提及的“一实施方式(one embodiment)”、“特定实施方式”、“一或多个实施方式”或“实施方式(an embodiment)”，意味着与实施方式关联描述的特定特征、结构、材料、或特性被包括在本发明的至少一个实施方式中。因此，在整个说明书的各种地方出现的诸如“在一或多个实施方式中”、“在特定实施方式中”、“在一实施方式中(in oneembodiment)”或“在一实施方式中(in an embodiment)”的词组并不必然意指本发明的同一个实施方式。再者，特定特征、结构、材料、或特性可以任何合适方式结合在一或多个实施方式中。
尽管在此已经参照特定实施方式描述本发明，但将理解到这些实施方式仅是对本发明的原理与应用的说明。对于本领域技术人员显而易见的是：在不背离本发明的精神与范围的情况下，可对本发明的方法与设备进行各种修改与变型。因此，本发明意欲包括涵盖在随附的权利要求及其等效形式的范围内的修改与变型。

Claims (15)

1.一种形成触点线的方法，所述方法包含以下步骤：
提供具有沟槽的基板表面，且所述沟槽中具有钴；
清洁所述钴的表面；和
在所述钴的所述表面上形成保护层，所述保护层包含硅化物或锗化物中的一或多种。
2.如权利要求1所述的方法，其中清洁所述钴的所述表面的步骤包含：在H2中烘烤所述基板。
3.如权利要求1所述的方法，其中清洁所述钴的所述表面的步骤包含：将所述基板暴露于H2等离子体。
4.如权利要求1所述的方法，其中清洁所述钴的所述表面的步骤包含：以氩等离子体溅射所述钴的所述表面。
5.如权利要求4所述的方法，其中所述氩等离子体进一步包含：超过约0.5原子百分比的含量的多个额外元素。
6.如权利要求1至5任一项所述的方法，其中形成所述保护层的步骤包含：形成钴硅化物。
7.如权利要求6所述的方法，其中形成所述钴硅化物的步骤包含：在范围为约200℃至约600℃的温度，将所述钴浸泡在含硅化合物中。
8.如权利要求7所述的方法，其中所述含硅化合物包含：硅烷、二硅烷、三硅烷、四硅烷、更高级的硅烷或硅基卤化物(silyl halide)中的一种或多种。
9.如权利要求8所述的方法，其中所述硅基卤化物实质上不包含氟原子。
10.如权利要求6所述的方法，其中在没有等离子体暴露下形成硅化物。
11.如权利要求1至5任一项所述的方法，其中形成所述保护层的步骤包含：在范围为约200℃至约600℃的温度，将所述钴浸泡在含锗化合物中。
12.如权利要求11所述的方法，其中所述含锗化合物包含：锗烷、二锗烷、三锗烷、四锗烷、更高级的锗烷或锗卤化物的一种或多种。
13.如权利要求1至5任一项所述的方法，其中形成所述保护层发生在范围为约0.5至约100托的压力。
14.如权利要求1至5任一项所述的方法，进一步包含以下步骤：退火具有所述保护层的所述基板，其中退火步骤包含：将所述基板暴露于在范围为约300℃至约600℃的温度的退火环境，所述退火环境包含Ar、N2、Ar/H2、N2/H2、H2、He或NH3。
15.如权利要求1至5任一项所述的方法，进一步包含以下步骤：在所述基板上沉积钴膜于所述保护层上方，通过CVD或PVD中的一种或多种沉积所述钴膜，且可选的退火以回流(reflow)所述钴膜。
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