CN1716548A - 掺杂的氮化物膜、掺杂的氧化物膜、以及其它掺杂的膜 - Google Patents

掺杂的氮化物膜、掺杂的氧化物膜、以及其它掺杂的膜 Download PDF

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CN1716548A
CN1716548A CNA2005100809411A CN200510080941A CN1716548A CN 1716548 A CN1716548 A CN 1716548A CN A2005100809411 A CNA2005100809411 A CN A2005100809411A CN 200510080941 A CN200510080941 A CN 200510080941A CN 1716548 A CN1716548 A CN 1716548A
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film
precursor
silicon
germanium
silicon nitride
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CN100428424C (zh
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阿施马·B·查克拉瓦尔蒂
贾德森·霍尔特
凯文·K·常
萨达南德·V·德什潘德
兰加拉詹·加甘纳桑
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Core Usa Second LLC
GlobalFoundries Inc
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International Business Machines Corp
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Abstract

在氮化硅、氧化硅、氮氧化硅、或碳化硅膜的形成过程中加入至少一种非硅前体(例如锗前体、碳前体等)，改善了淀积速率和/或使得有可能调节膜的性质，例如调节膜的应力。而且，在掺杂的氧化硅或掺杂的氮化硅或其它的掺杂的结构中，掺杂剂的存在可以被用来测量与掺杂剂相关的信号作为腐蚀过程中的腐蚀停止或其它用来达到控制。

Description

掺杂的氮化物膜、掺杂的 氧化物膜、以及其它掺杂的膜
技术领域
本发明一般涉及到用来制造半导体器件的薄膜，特别是涉及到氮化物膜和氧化物膜。
背景技术
为了改善互补金属氧化物半导体(CMOS)器件中的驱动电流，应力膜已经被用作隔垫或线条中间(MOL)的衬里(也称为预置金属介质(PMD)衬里)。导致高度拉伸或高度压缩的氮化物膜的淀积方法是众所周知的(例如快速热化学气相淀积(RTCVD)、等离子体增强化学气相淀积(PECVD)、采用诸如硅烷(SiH4)、二氯硅烷(DCS)、乙硅烷、六氯乙硅烷、二叔丁基氨基硅烷(BTBAS)、以及氨气(NH3)之类的硅(Si)前体的高密度等离子体(HDP))。但在给定的淀积方法中，仅仅有可能在小范围内调制应力。要大范围内调制应力而不牺牲薄膜质量，是非常困难的。
而且，对于由引入硅的氮化(NiSi)工艺而驱动的MOL的在较低温度下淀积的氮化物膜/氧化物膜，存在子越来越大的需求。已经研究了许多低温前体，尚未证明有理想的。
典型地说，在LPCVD炉子中，DCS和NH3被用来在700℃和以上的温度下淀积氮化硅膜。
发明内容
因此，本发明的目的是提供比常规工艺提高了的淀积速率，从而提供更多的可制造的膜，特别是氮化硅膜、氧化硅膜、氮氧化硅膜、以及碳化硅膜。
本发明的另一目的是提供产生应力水平变化的质量良好的氮化物膜，从而以“插入”办法，亦即无需改变整体而增强器件性能的能力。
本发明的另一目的是降低氮化硅膜、氧化硅膜、氮氧化硅膜、或碳化硅膜的淀积温度。
本发明的再一目的是在氮化硅膜、氧化硅膜、氮氧化硅膜、或碳化硅膜的产生过程中控制锗的加入，以便控制产生的膜中的应力。
本发明的一个优选实施方案是这样一种工艺，其中，淀积了至少一种硅前体，加入了至少一种锗前体和/或至少一种碳前体，以便产生具有可调应力的掺锗和/或掺碳的氮化硅膜或氧化硅膜。
于是，在淀积膜的过程中，利用调整至少一种前体就可以调节被产生的氮化硅膜或氧化硅膜的至少一种化学或物理性质(例如应力性质)。
有利的是，根据本发明，在氮化硅膜、氧化硅膜、氮氧化硅膜、或碳化硅膜的淀积中，能够得到比常规温度低的淀积。
本发明的一个优选实施方案提供了一种产生掺杂的氮化物膜、掺杂的氧化物膜、掺杂的氮氧化物膜、或掺杂的碳化物膜的方法，此方法至少包含：提供至少一种硅前体(例如SiH4、DCS、BTBAS、HCD、乙硅烷、丙硅烷等)；提供氮前体(可以与硅前体相同或不同)或氧前体中的至少一种；进一步提供至少一种非硅前体(可以与硅前体、氮前体、和/或氧前体相同或不同)；其中，掺杂的氮化物膜、掺杂的氧化物膜、掺杂的氮氧化物膜、或掺杂的碳化物膜被形成(倘若此膜是掺杂的氧化物时，则非硅前体不是硼和磷)。
用于本发明方法的非硅前体是例如锗前体(例如有机锗化合物等、GeH4、GeH3CH3等)、碳前体(例如C2H4等)；双硼烷；铝前体(例如三甲基铝(TMA)、AlH3、异丙氧化铝等)；硼前体；砷前体、铪前体；镓前体(例如三甲基镓、三烷基氨基镓、GaH3等)；铟前体(例如三甲基铟、三烷基氨基铟、InH3等)；等等。此外，锗、碳、硼、铝、砷、铪、镓、铟等的烷基氢化物或烷基氨基氢化物可以被用作前体。在本发明的一个特别优选的实施例中，同时以提供气流的形式来提供至少一种硅前体和至少一种非硅前体。
本发明的方法可以用来产生各种掺杂的膜，例如掺锗和/或掺碳的氮化硅、氧化硅、氮氧化硅、或碳化硅膜等；具有可调应力的氮化硅、氧化硅、氮氧化硅、或碳化硅膜；具有均匀分布的掺杂剂浓度的掺杂氮化硅膜(例如具有均匀分布的锗浓度的掺锗的氮化硅膜)；等等。根据本发明方法的一个实施例是例如将锗(锗前体)加入到硅烷和氨气的混合物，并形成掺锗的氮化硅膜。
在本发明方法的另一优选实施方案中，可以采用前体调整(例如至少二种前体的混合物等)，以便调节产生的膜的至少一种化学或物理性质(例如产生的膜的应力；湿法腐蚀速率；干法腐蚀速率；腐蚀终点；淀积速率；物理、电学、和/或光学性质等)。
本发明的方法还可以可选地包含从非硅前体测量非硅掺杂剂的信号，所述信号测量是为了控制腐蚀。
在本发明方法的某些实施方案中，可以在比省略了非硅前体时更低的温度下，例如在低于大约700℃的淀积温度(包括但不局限于低达室温的淀积温度)下有利地进行淀积。可以采用本发明方法所用淀积的优选实施例，是例如RTCVD、PECVD、LPCVD、远距离等离子体氮化物(remote plasma nitride)、原子层淀积(ALD)等。
本发明的其它优选实施方案提供了一些膜，例如在3GPa(压缩)-3GPa(拉伸)范围内具有可调应力的氮化硅、氧化硅、氮氧化硅、或碳化硅膜(例如掺锗的膜等)；氮化硅膜，其中的膜是具有均匀分布的锗的掺锗的氮化硅膜；掺铝的氧化硅膜；掺锗的氮化硅膜等；掺锗的膜，其中，掺锗膜的应力至少比用除了没有锗掺杂之外其它都相同的工艺已经形成的膜的应力大约大1.0GPa(优选为1.2GPa)。
本发明的膜可以包括一种或多种掺杂剂，例如多重掺杂剂。用于本发明的膜的掺杂剂的例子包括例如锗(Ge)、碳(C)、硼(B)、铝(Al)、镓(Ga)、铟(In)等，这些掺杂剂可以单独使用或组合使用。
附图说明
参照附图，从本发明优选实施方案的下列详细描述中，可以更好地理解上述和其它的目的、情况、以及优点，其中：
图1是一个氮化硅膜和二个LPCVD SiGe氮化物膜的椭圆测量(49点)图。
图2是根据49点椭圆测量得到的一个氮化硅膜和二个SiGe氮化物膜的腐蚀速率图，图2涉及到图1所示的膜。
图3是淀积速率与锗加入的函数关系图，曲线表示了有锗和无锗的情况，图3涉及到图1所示的膜。
图4是侧视图，示出了根据本发明一个实施方案的受应力的衬里，此受应力的衬里与隔垫、栅、以及沟道一起使用。
图5A-5C示出了根据本发明一个实施方案的终点探测方法
具体实施方式
在本发明中，在产生掺杂的氮化物膜、掺杂的氧化物膜、掺杂的氮氧化物膜、或掺杂的碳化物膜的过程中，至少控制淀积速率以及形成的膜的化学和/或物理性质(例如可调应力)之一。借助于引入并非用来产生氮化物膜、氧化物膜、氮氧化物膜、或碳化物膜的传统试剂的额外的非硅前体，来实现这一控制，此额外的非硅前体是锗前体和碳前体。
借助于在诸如淀积氮化物膜、淀积氧化物膜、淀积氮氧化物膜、或淀积碳化物膜之类的淀积工艺中包括非硅前体掺杂剂(例如锗前体等)，本发明实现了这些优点。
例如，在一个实施方案中，借助于将锗加入到氮化物膜、氧化物膜、氮氧化物膜、以及碳化物膜的淀积中，特别是掺杂的氮化物膜或氧化物膜中，本发明使得能够低温淀积氮化物膜、氧化物膜、氮氧化物膜、和/或碳化物膜。本发明人发现了下列事实，即能够在比硅外延更低的温度下完成硅锗(SiGe)外延，并进一步发现锗前体加入到硅前体中，降低了膜的淀积温度。
用于本发明的锗前体可以是例如授予Bensahel等人(法国Telecom)的2002年8月6日发布的美国专利6429098和2000年9月12日发布的美国专利6117750中或授予Reinberg(MicronTechnology公司)2001年7月10日发布的美国专利6258664中所述的锗前体之类的熟知的锗前体。这些锗前体可以在市场上得到。用于本发明的锗前体的一个例子是GeH4。
本发明在氮化物、氧化物、氮氧化物、碳化物等的淀积中使用了至少一种锗前体，若有需要，此淀积可以是低温淀积，例如700℃或以下例如室温和其它温度下的淀积。在一个优选实施例中，本发明的方法可以在室温下于P3I等离子体浸入装置中进行以便淀积氮化物。
倘若在用来产生氮化物膜、氧化物膜、氮氧化物膜、或碳化物膜的本发明中包括非硅前体，则可以常规地进行有关于各个组成部分的其它方面的生产工艺，例如用氮前体(例如NH3等)和硅前体(例如DCS等)。为了产生氮化硅膜，就包括氮前体。为了产生氧化硅膜，就包括氧前体。为了产生氮化硅膜或氧化硅膜，就包括硅前体。可以理解的是，硅前体可以与氮化物或氧化物前体不同或相同。例如，BTBAS可以用作硅前体和氮前体。在本发明的一些实施方案中，试剂(例如BTBAS等)可以可选地用作二种或多种前体。
根据本发明用锗前体和/或碳前体形成氮化物、氧化物、氮氧化物、或碳化物的示例性温度优选为低于700℃，低于650℃更优选，500℃或以下的温度甚至更优选。例如，在锗掺杂的情况下，500℃或以下的有利温度可以被用来淀积掺锗的氮化硅膜。可以理解的是，虽然本发明有利地使得有可能实现所希望的比较低的淀积温度，但并不一定要求在所有实施方案中采用低的淀积温度，例如，根据本发明，可以在各种淀积温度下对膜进行有利的应力调节。
所述用于本发明的非硅前体不受特别的限制，作为例子可以指出锗前体、碳前体、铝前体、硼前体、砷前体、铪前体、镓前体、铟前体、以及其它各种掺杂剂前体。
本发明还可以应用于MOL势垒技术。例如众所周知，MOL势垒氮化物能够提高器件的可靠性(负偏置温度不稳定性等)。本发明利用锗前体和/或碳前体，提供了调节采用不同前体组合的势垒氮化物膜的化学和/或物理性质的能力。这种能力可以被用来获得显著的器件可靠性提高。
根据本发明产生的膜的厚度不受特别的限制，可以根据应用来选择厚度。膜的厚度可以从薄端(例如500埃、10埃、或更薄)到厚端(例如1000埃、5000埃、或更厚)，以及约为10-5000埃的厚度，以及视应用要求而定的更薄或更厚。
根据本发明制作的膜的掺杂剂浓度不受特别的限制，可以按需要调节。掺杂剂(例如锗等)浓度的一个例子是大约1-10％，在另一例子中约为1-50％。
本发明包括一个实施方案，其中使用了多重非硅前体，例如锗前体和碳前体；锗前体和硼前体等。例如，在氮化硅膜或氧化硅膜的淀积过程中加入多重前体，可以提供所希望的增强效应。
本发明可以被用来探测腐蚀终点。例如，当执行常规的氮化硅腐蚀时，存在着需要在氮化硅终点处停止腐蚀而不过腐蚀到硅的问题。但这种腐蚀终点常常不陡峭，用常规方法常常会腐蚀到硅中。利用本发明，若采用掺杂的氮化硅(例如掺锗的氮化硅)，利用光发射谱来探测锗(例如可以寻找氟化锗信号)，则锗在氮化硅中的存在可以被用来提供腐蚀终点的信号，从而有利地防止过度腐蚀。
上述这种腐蚀停止例子不受限制，本发明扩展到在掺杂的氮化物膜或掺杂的氧化物膜中使用各种掺杂剂信号。例如，可以提供掺杂的薄氮化硅层作为腐蚀停止层(例如掺锗的氮化硅层等)，并可以监测掺杂剂信号(例如锗信号等)，来确定此层开始于何处。可以在腐蚀方面提供本发明的一些不同的实现方法。另一例子是掺锗氮化物下方的一种掺碳或掺硼的氧化物薄层。对于这种结构，可以监测锗信号的下降和碳信号的出现，以便得到更好的腐蚀结果。在腐蚀工艺中使用本发明的另一例子是采用二种不同的掺杂剂，例如在各个不同的层中提供一种掺杂剂，或在同一个层中提供二种不同的掺杂剂。可以理解的是，本发明包括了使用被控制的不同的信号，以便得到最大的灵敏度，且上面所述仅仅是一些例子。
本发明的另一种用途是，与其中不包括掺杂剂的膜相比，借助于包括掺杂剂而改变产生的膜(例如氮化硅和氧化硅)的应力。例如，对于氮化硅膜的情况，已经发现锗掺杂剂的出现将膜的应力改变到了拉伸区域。RTCVD氮化硅膜通常具有约为1-1.5GPa的(张)应力。在氮化硅膜中包括锗则提供了膜应力显著升高的改变，例如掺锗的氮化硅膜具有超过1.5GPa的(张)应力，例如2GPa或以上的(张)应力。当在同一个应力装置上测量根据本发明的掺杂膜以及不掺杂的比较膜时，可以在掺杂的膜中得到1GPa或以上的增量(优选为例如1.2GPa或以上的增量)。而且，本发明可以被用来将膜的应力从压应力改变到张应力，这标志着膜性质的一种显著改变。
于是，本发明可以被有利地用来按需要调节氮化硅或氧化硅膜或氮氧化硅或碳化硅膜的应力。
而且，本发明可以被用来产生掺杂的氮化硅膜、掺杂的氧化硅膜、掺杂的氮氧化硅膜、以及掺杂的碳化硅膜，例如掺锗的氮化硅膜、掺铝的氧化硅膜、掺硼的氮化硅膜等。
实施例1：在LPCVD炉子中，GeH4分别在二个不同的温度700℃和650℃下被加入到DCS和NH3的混合物中。还在780℃下淀积了一个标准的氮化硅膜作为对照。这样淀积了二个掺锗的氮化硅膜和一个标准的氮化硅膜。结果被总结在图1、2、3中。
在图1中，顶部的曲线是以DCS/NH3＝0.3，在785℃下淀积的膜的曲线。图1中的中间曲线是以(DCS+Ge)/NH3＝0.3以及以Ge/DCS＝0.25，在700℃下淀积的膜的曲线。图1中的底部曲线是以与700℃下淀积的膜相同的比率，在650℃下淀积的膜的曲线。
从图3可见，借助于将GeH4加入到工艺气体，已经得到了淀积速率的显著提高。而且，此实施例1的掺锗膜具有相似于标准的高温膜的性质(由湿法腐蚀速率确定的)。
锗烷在硅前体和氨气的混合物中的加入，使得：能够提高现有工艺的淀积速率，使工艺的制造能力更强；能够降低工艺的淀积速率，使之可扩展到未来的技术；和/或能够控制形成的膜的应力。
实施例2：重要的是，本发明已经认识到可以利用在氮化物膜形成过程中加入锗来调整膜中的应力。对于硅衬底，可以考虑下述结果：(i)Si-N膜的应力为每平方厘米4×109达因(压缩)；(ii)SiGe-N膜的应力为每平方厘米8.2×109达因(拉伸)。
如上述数据所示，在常规氮化硅膜与本发明的掺锗的氮化硅膜之间，存在着接近一个数量级的应力差别。
可以理解的是，本发明在淀积速率和/或应力调节方面的优点不局限于氮化物膜，而是可适用于氧化物膜(例如氧化硅膜等)以及其它的膜，例如其它的非晶膜。
实施例3：锗被加入到硅烷和氨气的混合物中，形成了掺锗的氮化硅膜。与同等的无锗烷工艺相比，锗烷工艺的淀积速率被提高了。对于无锗工艺，产生的膜的应力是0.4GPa(压应力)。对于采用锗的本发明的工艺，应力是0.8GPa(张应力)。这样，根据本发明采用锗，就得到了1.2GPa的应力改变，这是一个很大的改进。
实施例4：参照图4，示出了根据本发明一个实施方案的受到应力的膜的一个例子。受到应力的氮化物衬里40(根据本发明产生的)被示为与隔垫41，具有层44(硅化物)且位于沟道(SOI)上的(多晶)栅一起使用。
实施例5：参照图5A-5C，示出了根据本发明用于终点探测的反掺杂的氮化物和氧化物层的例子。参照图5A，在包括栅52的器件中，在氮化物或氧化物层50(具有第二掺杂剂)上提供了隔垫氮化物51(具有第一掺杂剂)。图5A的淀积后膜根据图5B所示的初始RIE步骤被加工，其中，在初始RIE过程中，第一掺杂剂被探测。接着，如图5C所示执行最终RIE步骤，其中，腐蚀终点被达到。在最终RIE步骤中，(隔板氮化物51或被腐蚀的隔板氮化物51’中的)较少量的第一掺杂剂被探测，并开始探测(氮化物或氧化物层50中的)第二掺杂剂。在腐蚀终点步骤之后，保留了被可控地腐蚀的隔垫氮化物51’。
虽然就其优选实施方案已经描述了本发明，但本技术领域的熟练人员可以理解的是，可以利用所附权利要求的构思与范围内修正来实施本发明。

Claims (28)

1.一种制作掺杂的氮化硅膜、掺杂的氧化硅膜、掺杂的氮氧化硅膜、或掺杂的碳化硅膜的方法，此方法至少包含：
提供至少一种硅前体，
提供氮前体或氧前体中，所述氮前体可以与硅前体相同或不同的至少一种，
进一步提供至少一种非硅前体，所述非硅前体可以与硅前体、氮前体、和/或氧前体相同或不同，
其中，掺杂的氮化硅膜、掺杂的氧化硅膜、掺杂的氮氧化硅膜、或掺杂的碳化硅膜被形成，只要在此膜是掺杂的氧化物时非硅前体不是硼和磷。
2.权利要求1的方法，其中，同时以提供气流的形式来提供所述至少一种硅前体和提供所述至少一种非硅前体。
3.权利要求1的方法，其中，所述非硅前体是锗前体。
4.权利要求1的方法，其中，所述非硅前体选自碳前体、硼前体、铝前体、砷前体、铪前体、镓前体、以及铟前体。
5.权利要求1的方法，其中，所制作的膜是氮化硅膜。
6.权利要求1的方法，其中，所制作的膜是掺锗的和/或掺碳的氮化硅或氧化硅。
7.权利要求1的方法，其中，所制作的膜具有可调的应力。
8.权利要求1的方法，其中，所述非硅前体是
有机锗化合物或选自GeH4和GeH3CH3的锗前体；
双硼烷；
三甲基铝(TMA)；
C2H4碳前体；
三甲基镓；
三甲基铟；
三烷基氨基镓；
三烷基氨基铟；
GaH3；
InH3；
AlH3；以及
异丙氧化铝。
9.权利要求1的方法，其中，所述非硅前体是锗、碳、硼、铝、砷、铪、镓、或铟的烷基氢化物或烷基氨基氢化物。
10.权利要求1的方法，它包括采用前体调整来调节所制作的膜的至少一种化学或物理性质。
11.权利要求10的方法，其中，所述前体调整是至少二种前体的混合物。
12.权利要求10的方法，其中，所述至少一种化学或物理性质是所制作的膜的应力。
13.权利要求10的方法，其中，所述至少一种化学或物理性质选自：湿法腐蚀速率；干法腐蚀速率；腐蚀终点；淀积速率；物理、电学、和/或光学性质。
14.权利要求1的方法，其中，在比省略了非硅前体时更低的温度下进行淀积。
15.权利要求1的方法，在低于大约700℃的温度下进行。
16.权利要求1的方法，其中所述淀积是RTCVD、PECVD、LPCVD、远距离等离子体氮化物、或ALD。
17.权利要求1的方法，它包括将锗烷加入到硅烷和氨气的混合物中，并形成掺锗的氮化硅膜。
18.权利要求1的方法，还包含测量来自非硅前体的非硅掺杂剂信号的步骤，所述信号测量是为了控制腐蚀。
19.权利要求1的方法，其中，所制作的膜是具有均匀分布的锗浓度的掺锗的氮化硅膜。
20.一种氮化硅或氧化硅膜，具有在大约3GPa(压缩)-3GPa(拉伸)范围内可调节的应力。
21.权利要求20的膜，其中所述膜是掺锗的。
22.权利要求20的膜，其中所述膜是掺硼的、掺铝的、掺碳的、掺砷的、掺铪的、掺镓的、和/或掺铟的。
23.权利要求20的膜，它包括二种或多种掺杂剂。
24.权利要求20的膜，其中所述膜是掺锗的，并且其中所述掺锗膜的应力比除了没有锗掺杂之外采用相同的工艺制作的膜的应力大至少约1.0GPa。
25.一种掺铝的氧化硅膜。
26.一种掺锗的氮化硅膜。
27.权利要求26的膜，其中所述膜是具有均匀分布的锗的掺锗氮化硅膜。
28.权利要求1的方法，其中，在室温下进行淀积。
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