CN102741989A - 固化无碳可流动cvd膜 - Google Patents

固化无碳可流动cvd膜 Download PDF

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CN102741989A
CN102741989A CN2010800564165A CN201080056416A CN102741989A CN 102741989 A CN102741989 A CN 102741989A CN 2010800564165 A CN2010800564165 A CN 2010800564165A CN 201080056416 A CN201080056416 A CN 201080056416A CN 102741989 A CN102741989 A CN 102741989A
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carbon
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梁璟梅
洪锡湲
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Applied Materials Inc
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Abstract

本发明描述了一种用来形成氧化硅层的方法。所述方法可以包括以下步骤：将无碳的含硅前体与自由基-氮-和/或-氢前体混合，并在基材上沉积含硅-氮-和-氢的层。然后通过在含臭氧的气氛中进行低温退火(“固化”)来引发所述含硅-氮-和-氢的层向含硅和氧的层转化。所述在含臭氧气氛中进行的硅和氮膜向氧化硅的转化可能是不完全的，在含氧气的气氛中补充进行较高温度的退火。

Description

固化无碳可流动CVD膜
相关申请的交叉引用
本申请是2010年9月28日提交的名为“固化无碳可流动CVD膜(CURINGNON-CARBON FLOWABLE CVD FILMS)”的美国专利申请第12/891,937号的PCT申请，要求Jingmei Liang等人在2009年11月12日提交的名为“固化无碳可流动CVD膜(CURING NON-CARBON FLOWABLE CVD FILMS)”的美国临时专利申请第61/260,568号的权益,这些文献全文都参考结合入本文中。
发明背景
自从半导体装置引进数十年以来，其几何尺寸已经显著减小。现代半导体制造设备经常制造特征尺寸为45纳米、32纳米和28纳米的装置，人们正在开发新的设备，用来制造具有更小几何结构的装置，并且将这些新的设备投入使用。特征尺寸的减小导致装置上的结构特征的空间尺度减小。所述装置上的间隙和沟槽的宽度减小到了一定的程度，使得间隙深度和宽度的纵横比高到足以使得用介电材料填充间隙造成困难。在沉积介电材料的时候，容易在间隙被完全填充之前，在顶部造成堵塞，在间隙的中部产生空隙或缝隙。
这些年来，人们开发了许多技术来避免介电材料堵塞间隙顶部,或者“修复”已经形成的空隙或缝隙。一种方法是使用高流动性的前体材料，将液相状态的所述材料施加于旋转的基材表面(例如SOG沉积技术)。这些可流动的前体能够流入极小的基材间隙中并填充这些间隙，同时不会形成空隙或者不牢固的缝隙。但是，一旦这些高流动性的材料沉积，则必须使其硬化，形成固体介电材料。
在许多的情况下,所述硬化过程包括采用热处理从沉积的材料中除去碳和羟基，留下固体电介质如氧化硅。不幸的是，碳和羟基的除去经常会在硬化的电介质中留下孔穴，所述孔穴会降低最终材料的质量。另外，所述硬化电介质操作还容易造成体积收缩，会在电介质与周围基材之间的界面处留下裂纹和空间。在一些情况下，所述硬化电介质的体积可以减小40％或者更多。
因此，人们需要新的沉积方法和材料，在结构化基材上形成介电材料，同时不会在基材的间隙和沟槽中形成空隙和/或缝隙。人们还需要用来对可流动的介电材料进行硬化的材料和方法，同时产生更少的孔穴，并且体积的减小程度更小。本发明解决这些需求以及其它需求。
发明概述
本发明描述了一种用来形成氧化硅层的方法。所述方法可以包括以下步骤：将无碳的含硅前体与自由基-氮-和/或-氢前体混合，并在基材上沉积含硅-氮-和-氢的层。然后通过在含臭氧的气氛中进行低温退火(“固化”)来引发所述含硅-氮-和-氢的层向含硅和氧的层转化。所述在含臭氧气氛中进行的硅和氮膜向氧化硅的转化可能是不完全的，在含氧气氛中补充进行较高温度的退火。
本发明的实施方式包括在基材加工室的无等离子体基材加工区之内，在基材上形成含硅和氧的层的方法。所述方法包括在所述基材上沉积无碳的含硅-氮-和-氢的层。所述方法还包括在含臭氧的气氛中，使得所述含硅-氮-和-氢-的层固化，使得所述含硅-氮-和-氢的层转化为氧化硅层。
在下文中列出了本发明的一部分实施方式和特征,另外，本领域技术人员通过阅读说明书或者实施本发明，可以了解到本发明的另外一部分实施方式和特征。通过说明书中所述的手段、组合和方法能够实现和获得本发明的特征和优点。
附图简要说明
通过参考说明书的剩余部分和附图，可以进一步了解本发明的性质和优点，在图中，相同的编号表示类似的对象。在一些情况下，编号包括用连字号相连的下标，用来表示多种类似的对象。当描述没有下标的编号的时候，表示所有的多种类似的对象。
图1是根据本发明一些实施方式用来制造氧化硅膜的选定步骤的流程图。
图2是根据本发明一些实施方式用来在基材间隙中形成氧化硅膜的选定步骤的另一流程图。
图3是根据本发明一些实施方式用来使得旋涂介电膜固化的选定步骤的另一流程图。
图4显示根据本发明实施方式的基材加工系统。
图5A显示根据本发明实施方式的基材加工室。
图5B显示根据本发明实施方式的气体分布莲蓬头。
具体实施方式
本发明描述了一种用来形成氧化硅层的方法。所述方法可以包括以下步骤：将无碳的含硅前体与自由基-氮-和/或-氢前体混合，并在基材上沉积含硅-氮-和-氢的层。然后通过在含臭氧的气氛中进行低温退火(“固化”)来引发所述含硅-氮-和-氢的层向含硅和氧的层的转化。所述在含臭氧的气氛中进行的硅和氮膜向氧化硅的转化可能是不完全的，在含氧气氛中补充进行较高温度的退火。
虽然不希望用尚不了解正确与否的假想理论来约束权利要求书的范围，但是进行一定的详细讨论总是有益的。与在含氧气的环境中、在较高基材温度下对基材仅进行退火的做法相比，通过在保持较低的基材温度的条件下，使得沉积的含硅-氮-和-氢的膜接触臭氧，可以提高氧含量。这可能是由于通过将自由基氮前体与无碳含硅前体混合来沉积硅-氮膜产生了相对开放的网络。所述开放的网络能够使得臭氧更深地渗入膜内,使得氧化物转化沿着基材的方向延伸。如果在高温条件下进行所述转化，可能会使得表面附近的网络闭合，由此限制转化的物理程度。
臭氧的反应活性介于分子氧和原子氧之间。分子氧需要较高的温度以使得氧化反应活化，这会导致表面附近开放的硅-氮网络闭合。这种闭合会对所述含硅-氮-和-氢的层较深的部分的氧化构成不利的限制。原子氧在低温条件下过于容易反应，也会使得网络闭合。我们发现臭氧能够提供稳定性，以便深深地渗入开放的网络中，同时不需要高温来促进氧化。下面将对形成氧化硅层的方法和体系的其它细节进行描述。
示例性的氧化硅形成工艺
图1是根据本发明一些实施方式，用来制造氧化硅膜的方法100中选定步骤的流程图。所述方法100包括向基材加工区域102提供无碳硅前体。所述无碳硅前体可以是例如硅-氮前体、硅-氢前体、或者含硅-氮前体，以及其它种类的硅前体。所述硅前体除了是无碳的以外，还可以是无氧的。由于缺少氧，会导致由所述前体形成的硅-氮层中硅羟基(Si-OH)的浓度较小。如果沉积的膜中硅羟基过多，会导致在用来从沉积的层中除去羟基(-OH)的沉积后步骤中，孔隙率和收缩程度增大。
无碳硅前体的具体例子可以包括甲硅烷基胺，例如H2N(SiH3),HN(SiH3)2和N(SiH3)3,以及其它的甲硅烷基胺。在不同的实施方式中，甲硅烷基胺的流速可以大于或等于约200sccm,大于或等于约300sccm，或者大于或等于约500sccm。本文给出的所有的流速针对双室基材加工系统。单晶片系统需要将所述流速减半，其它的晶片尺寸需要将流速按照处理面积按比例变化。可以将这些甲硅烷基胺与其它的气体混合，所述其它的气体可以作为载气和/或反应气体。其它的气体的例子包括H2,N2,NH3,He和Ar,以及其它的气体。无碳硅前体的例子还可以包括单独使用或者与其它的含硅(例如N(SiH3)3)气体、含氢(例如H2)气体和/或含氮(例如N2,NH3)气体混合使用的硅烷(SiH4)。无碳硅前体还可以包括乙硅烷、丙硅烷、甚至更高级的硅烷,以及氯代硅烷,这些硅烷单独使用，或者与另外的或者前述的无碳硅前体组合使用。
还可以向所述基材加工区域104提供自由基-氮前体。所述自由基-氮前体是由更稳定的氮前体在所述基材加工区域之外产生的含氮-自由基的前体。例如，包含NH3、肼(N2H4)和/或N2的稳定的氮前体化合物可以在所述加工室之外的室等离子体区域或者远程等离子体系统(RPS)中活化，形成自由基-氮前体,然后将所述自由基-氮前体传输到所述基材加工区域之内。在不同的实施方式中，所述稳定的氮前体还可以是包括以下物质的混合物：NH3&N2,NH3&H2,NH3&N2&H2以及N2&H2。在含N2和H2的混合物中，还可以使用肼代替NH3，或者将肼与NH3组合使用。在不同的实施方式中，稳定的氮前体的流速可以大于或等于约300sccm,大于或等于约500sccm，或者大于或等于约700sccm。在所述室等离子体区域中产生的自由基-氮前体可以是以下的一种或多种：·N,·NH,·NH2等等,还可以同时包含在等离子体中形成的离子化物质。还可以在远程等离子体中，将氧源与更稳定的氮前体合并，用来在减小流动性的同时对膜预加载氧。氧源可以包括以下的一种或多种：O2,H2O,O3,H2O2,N2O,NO或NO2。
在利用室等离子体区域的实施方式中,在基材加工区域的与沉积区域隔离的区段内产生所述自由基-氮前体，在所述沉积区域中，所述前体发生混合和反应，在沉积基材(例如半导体晶片)上沉积硅-氮层。所述自由基-氮前体还可以包括载气，例如氢气(H2),氮气(N2),氦气，等等。在本文中，在含硅-氮-和-氢的层的生长过程中，以及低温臭氧固化过程中，可以认为所述基材加工区域是“无等离子体的”。"无等离子体"不一定表示所述区域完全没有等离子体。等离子体在室等离子体区域内的边界很难限定，有可能通过莲蓬头中的孔侵入到基材加工区域上。对于感应耦合等离子体，例如可能会在基材加工区域内直接引发少量的离子化。另外,可以在基材加工区域内产生低强度等离子体，而不消除形成膜的可流动性。在形成自由基氮前体的过程中，等离子体的离子密度远小于室等离子区域的离子密度的所有原因都不会偏离本发明所述的“无等离子体”的范围。
在基材加工区域中,所述无碳硅前体和自由基-氮前体发生混合和反应，在沉积基材106上沉积含硅-氮-和-氢的膜。在一些实施方式中，所述沉积的含硅-氮-和-氢的膜可以与一些设定组合相一致的方式沉积。在其它的实施方式中,所述沉积的含硅-氮-和-氢的膜具有可流动的特性，这与常规氮化硅(Si3N4)膜沉积技术不同。所述成形的可流动性使得膜能够流入基材沉积表面上的窄的间隙沟槽中和其它的结构中。
所述流动性可能是由于将自由基-氮前体与无碳硅前体混合造成的各种性质带来的。这些性质可以包括沉积的膜中大量的氢组分以及/或者存在短链聚硅氮烷聚合物。在成膜过程中和成膜之后，这些短链生长并网络化，形成更致密的介电材料。例如，所述沉积的膜可以具有硅氮烷类的Si-NH-Si主链(即无碳Si-N-H膜)。当硅前体和自由基氮前体均为无碳形式的时候，沉积的含硅-氮-和-氢的膜也是基本不含碳的。当然,“无碳”不一定表示膜中不含痕量的碳。在前体材料中可能存在碳污染物，由此引入沉积的硅-氮前体中。但是，这些碳杂质的量远远小于在包括碳部分的硅前体(例如TEOS,TMDSO等)中发现的量。
在沉积含硅-氮-和-氢的层之后，可以在含臭氧的气氛108中使得沉积基材发生固化。所述固化操作减小膜中(包括沟槽中)氮的浓度，同时增大膜中(包括沟槽中)氧的浓度。所述沉积基材可以保持在基材加工区域中进行固化，或者可以将所述基材转移到不同的室，在所述不同的室引入含臭氧的气氛。在不同的实施方式中，所述基材的固化温度可以约等于或低于600°C,约等于或低于400°C,约等于或低于300°C,约等于或低于250°C,约等于或低于200°C，或者约等于或低于150°C。在不同的实施方式中，所述基材的温度可以约等于或高于室温(25°C),约等于或高于50°C,约等于或高于100°C,约等于或高于150°C，或者约等于或高于200°C。根据本发明其它的实施方式，可以将任意所述上限与任意下限合并，形成基材温度的其它范围。在一些实施方式中，在基材加工区域中不存在等离子体,以避免产生原子氧，所述原子氧会使得表面附近的网络闭合，阻碍表面下方的氧化。在一些所述的实施方式中，在固化步骤过程中，臭氧流入基材加工区域的流速(仅仅由臭氧贡献)可以约等于或大于500sccm,约等于或大于1slm,约等于或大于2slm，或者约等于或大于5slm。在一些所述的实施方式中，在固化步骤过程中，臭氧的分压可以约等于或大于20Torr,约等于或大于30Torr,约等于或大于50Torr，或者约等于或大于100Torr。在一些实施方式中，在一些条件下(例如基材温度为大约100-200℃的条件下)，发现所述转化基本完全，因此可能不需要在含氧气氛中进行较高温度的退火。在一些情况下，通过从约等于或低于250℃的温度升高到高于400℃的温度(例如550℃)，使得含硅-氮-和-氢的膜进一步向氧化硅膜转化。在升高的温度条件下(高于400℃)，通过向所述含臭氧的气氛添加水分(H2O)可以进一步提高向氧化硅膜的转化。
在含硅-氮的层固化之后，沉积基材可以在含氧气氛110中退火。当引入含氧气氛的时候，所述沉积基材可以保留在与用于固化的相同的基材加工区域中，或者可以将所述基材转移到不同的室，向不同的室中引入含氧气氛。所述含氧气氛可以包括一种或多种含氧气体，例如分子氧(O2),臭氧(O3),水蒸气(H2O),过氧化氢(H2O2)和氮的氧化物(NO,NO2,N2O等),以及其它的含氧气体。所述含氧气氛还可以包含自由基氧和氢氧自由基，例如原子氧(O),氢氧基(OH)等,这些自由基可以在远处产生，转移到所述基材室内。还可以包含含氧物质的离子。在不同的实施方式中，所述基材的氧退火温度可以约等于或低于1100°C,约等于或低于1000°C,约等于或低于900°C，或者约等于或低于800°C。在不同的实施方式中，所述基材的温度可以约等于或高于500℃,约等于或高于600℃,约等于或高于700℃，或者约等于或高于800°C。在所述的实施方式中，当所述含氧气氛中包含水蒸气的时候，基材温度约等于或高于100°C,约等于或高于200°C,约等于或高于300°C，或者约等于或高于400°C。类似地，根据本发明其它的实施方式，可以将任意所述上限与任意下限合并，形成基材温度的其它范围。
在氧退火过程中，在基材加工区域中可以存在或者不存在等离子体。进入所述CVD室的含氧气体可以包括一种或多种已经在进入所述基材加工区域之前活化(例如自由基化、离子化等)的化合物。例如，所述含氧气体可以包括自由基氧物质、氢氧自由基物质等，这些物质通过使得更稳定的前体化合物经过远程等离子体源，或者通过用莲蓬头(showerhead)与基材加工区域隔开的室等离子体区域而活化。所述更稳定的前体可以包括能够产生氢氧(OH)自由基和离子的水蒸气(H2O)和过氧化氢(H2O2),以及能够产生原子氧(O)自由基和离子的分子氧和/或臭氧。
所述固化和氧退火的含氧气氛提供氧，用来将含硅-氮-和-氢的膜转化为氧化硅(SiO2)膜。如前文所述，由于所述含硅-氮-和-氢的膜中缺少碳，因此最终氧化硅膜中形成的孔穴的数量少得多。还会导致在转化为氧化硅的过程中，膜体积减小(即收缩)的程度要更小。例如，由含碳的硅前体形成的硅-氮-碳层在转化为氧化硅的时候可能会收缩40体积%或更多,而基本无碳的硅-氮膜可能收缩大约15体积%或更少。
如上文所述，可以通过将自由基氮前体与各种无碳含硅前体组合来制备所述沉积的含硅-氮-和-氢的层。在一些实施方式中，所述无碳含硅前体可以是基本无氮的。在一些实施方式中,所述无碳含硅前体和自由基氮前体都包含氮。另一方面,在一些实施方式中，所述自由基前体可以基本无氮,所述含硅-氮-和-氢的层的氮可以由所述无碳含硅前体提供。因此，最一般来说,在本文中将自由基前体称作“自由基-氮-和/或-氢前体”，这表示所述前体包含氮和/或氢。类似地,将流入等离子体区域形成自由基-氮-和/或-氢前体的前体称作含氮-和/或-氢的前体。这些概括可以适用于本发明的所有实施方式。在一些实施方式中，所述含氮-和/或-氢的前体包括氢气(H2)，而自由基-氮-和/或-氢前体包括·H等。
下面来看图2，图2是根据本发明一些实施方式用来在基材间隙中形成氧化硅膜的方法200的选定步骤的另一流程图。所述方法200可以包括将包括间隙的基材转移到基材加工区域(操作202)。所述基材可以包括用于将基材上形成的装置部件(例如晶体管)间隔和构造的多个间隙。所述间隙的高度和宽度可以满足以下条件：高度与宽度的纵横比(AR，即H/W)远远大于1:1(例如等于或大于5:1,等于或大于6:1,等于或大于7:1,等于或大于8:1,等于或大于9:1,等于或大于10:1,等于或大于11:1,等于或大于12:1,等等)。在很多情况下，所述高AR是由于间隙宽度很小造成的，所述间隙宽度约为90-22纳米或更小(例如小于90纳米,65纳米,50纳米,45纳米,32纳米,22纳米，16纳米等)。
在所述基材加工区域中，无碳硅前体与自由基氮前体混合(操作204)。可以在所述基材上沉积可流动的含硅-氮-和-氢的层(操作206)。因为所述层是可流动的，其可以填充具有高纵横比的间隙，同时不会在填充材料中心的周围形成空隙或不牢固的缝隙。例如，如果使用可流动的材料进行沉积，比较不容易在完全填充之前在间隙的顶部造成永久性堵塞，从而在间隙的中部留下空隙。
然后对新沉积的含硅-氮-和-氢的层进行固化(操作208)，然后在含氧气氛中退火(操作210)，从而将含硅-氮-和-氢的层转化为氧化硅。可以在较高的基材温度条件下、在惰性环境中进一步进行退火(图中未显示)，以使得氧化硅层致密化。
通过在含氧气氛中对新沉积的含硅-氮-和-氢的层进行固化和退火，在基材(包括基材间隙208)上形成氧化硅层。在一些实施方式中,所述操作208和210的工艺参数范围与图1中关于操作108和110所述的范围相同。如上文所述,与那些使用含碳前体形成的类似的层相比(在热处理步骤之前，层中包含大量的碳)，所述氧化硅层的孔穴更少，体积减小程度更低。在许多的情况下,体积减小足够小(例如约等于或小于15体积%)，足以避免通过热处理后步骤对氧化硅收缩导致的间隙内形成的空间进行填充、修复、或者以其它方式进行消除。在一些实施方式中，所述沟槽中的氧化硅层基本不含孔穴。
图3是根据本发明一些实施方式，用来制造氧化硅膜的示例性方法中选定步骤的另一流程图。所述方法300可以包括将具有沟槽的图案化基材转移到旋涂介电(SOD)设备中。将无碳含硅-氮-和-氢的层倾倒在图案化的基材上，使得所述基材旋转，从而均匀地分布所述层(操作304)。新沉积的旋涂介电(SOD)层位于沟槽内，并且可以位于基材的其它区域上。所述SOD层包含硅和氮，在与操作108和208类似的条件下发生固化，从而引发SOD层氧化，形成氧化硅层。所述基材在含臭氧的环境中保持在相同的较低的温度下，以使得在更接近基材和沟槽内的位置发生氧化。在一些实施方式中，随后进行高温氧退火和更高温度的惰性退火，以对SOD层进行进一步氧化和致密化。
示例性的氧化硅沉积系统
用来实施本发明实施方式的沉积室可以包括高密度等离子体化学气相沉积(HDP-CVD)室,等离子体促进的化学气相沉积(PECVD)室,低于大气压的化学气相沉积(SACVD)室,热化学气相沉积室,以及其它种类的室。可以用来实施本发明的实施方式的CVD系统的具体例子包括CENTURA
Figure BDA00001755286200091
HDP-CVD室/系统,以及PECVD室/系统,可以购自美国加利福尼亚州圣克拉拉市(Santa Clara,Calif.)的应用材料有限公司(Applied Materials,Inc.)。
可以用于本发明的示例性方法的基材加工室的例子可以包括Lubomirsky等在2006年5月30日提交的名为“用于电介质间隙填充的加工室(PROCESSCHAMBER FOR DIELECTRIC GAPFILL)”的共同受让的美国临时专利申请第60/803,499号示出并描述的那些，该文献全文参考结合入本文中。其它的示例性系统可以包括美国专利第6,387,207号和第6,830,624号示出并描述那些，这些文献参考结合入本文中。
这些沉积系统的实施方式可以结合入用来制造集成电路芯片的更大型的制造系统中。图4显示根据所述实施方式的沉积、焙烧和固化室的系统400。在图中,一对FOUP(前部开口统一彀罩(unified pod))402供应基材(例如直径300毫米的晶片)，所述基材由自动臂404接收，放入低压保持区域406内，然后放入晶片加工室408a-f中的一个之内。可以用第二自动臂410将基材晶片从保持区域406输送到加工室408a-f以及送回。
所述加工室408a-f可以包括用来在基材晶片上沉积可流动介电膜并对该可流动介电膜进行退火、固化和/或蚀刻的一种或多种系统部件。在一种构型中,可以使用两对加工室(例如408c-d和408e-f)在所述基材上沉积可流动的介电材料,第三对加工室(例如408a-b)可以用来对沉积的电介质进行退火。在另一种构型中，可以设置相同的两对加工室(例如408c-d和408e-f)，用来在基材上沉积可流动的介电膜，并且对所述基材上的可流动介电膜进行退火,而第三对室(例如408a-b)可以用于沉积的膜的UV或电子束固化。在另一种构型中,全部三对室(例如408a-f)可以设置用来在基材上进行可流动介电膜的沉积和固化。在另一种构型中，两对加工室(例如408c-d和408e-f)可以用于可流动电介质的沉积以及紫外或电子束固化,而第三对加工室(例如408a-b)可以用来对介电膜进行退火。上述任意一种或多种工艺可以在不同实施方式所示的与制造系统隔开的室中实施。
另外，一个或多个加工室408a-f可以设置成湿处理室。这些加工室包括在含有水分的气氛中对可流动的电介质膜进行加热。因此，系统400的实施方式可以包括湿处理室408a-b和退火加工室408c-d，用来对沉积的介电膜进行湿退火和干退火。
图5A显示根据所述实施方式的基材加工室500。远程等离子体系统(RPS)510可以对气体进行处理，然后所述气体通过气体进入组件511。在所述气体进入组件511中可以观察到两个独立的供气通道。第一通道512承载那些通过远程等离子体系统RPS 510的气体,而第二通道513绕过RPS 500。在所述的实施方式中，第一通道502可以用于加工气体，而第二通道513可以用于处理气体。图中显示在盖子(或者传导性顶部部分)521和有孔的隔离件553之间具有绝缘环524,通过该绝缘环524可以相对于所述有孔的隔离件553对盖子521施加AC电势。加工气体通过第一通道512进入室等离子体区域520，可以单独地被室等离子体区域520内的等离子体激发，或者被室等离子体区域520和RPS510的组合内的等离子体激发。在本文中，将所述室等离子体区域520和/或RPS510的组合称为远程等离子体系统。所述有孔的隔离件(也称作莲蓬头)553将室等离子体区域520与所述莲蓬头553下方的基材加工区域570隔开。莲蓬头553使得室等离子体区域520中的等离子体不直接激发基材加工区域570中的气体,同时允许激发的物质通过室等离子体区域520进入基材加工区域570。
莲蓬头553位于室等离子体区域520和基材加工区域570之间，允许在室等离子体区域520中产生的等离子体流出物(前体或其它气体的激发的衍生物)通过横穿板厚度的多个通孔556。所述莲蓬头553还具有一个或多个空心体积551，所述空心体积中可以填充蒸气或者气体形式的前体(例如含硅前体)，通过小孔555进入基材加工区域570，而不是直接进入室等离子体区域520。在所述的实施方式中，莲蓬头553的厚度大于通孔556的最小直径550的长度。为了维持相当高浓度的激发物质从室等离子体区域520渗入基材加工区域570,通过形成部分通过莲蓬头553的通孔556的较大直径部分，限制所述通孔的最小直径550的长度526。在所述的实施方式中，所述通孔556的最小直径550的长度可以约等于或小于通孔556的最小直径。
在图中所示的实施方式中,当在室等离子体区域520中用等离子体进行激发的时候，所述莲蓬头553可以(通过通孔556)分配加工气体，所述加工气体包含氧、氢和/或氮和/或这种加工气体的等离子体流出物。在一些实施方式中,通过第一通道512引入RPS 510和/或室等离子体区域520的加工气体可以包含以下的一种或多种：氧气(O2),臭氧(O3),N2O,NO,NO2,NH3,NZxHy(包括N2H4),硅烷,乙硅烷,TSA和DSA。所述加工气体还可以包括载气，例如氦气、氩气、氮气(N2)等。所述第二通道513还可以用来输送加工气体和/或载气，和/或膜固化气体，所述膜固化气体用来从生长中的或者新沉积的膜中除去不希望有的组分。等离子体流出物可以包括加工气体的离子化衍生物或中性衍生物，在本文中也可以称作自由基-氧前体和/或自由基-氮前体，表示引入的加工气体的原子组分。
在一些实施方式中，通孔556的数量可以约为60-2000。通孔556可以具有各种形状，但是最方便的情况是制成圆形。在所述实施方式中，通孔556的最小直径550可以约为0.5-20毫米，或者约为1-6毫米。通孔的横截面形状还可以在一定的范围内选择，所述横截面形状可以是圆锥形、圆柱形、或者这两种形状的组合。在不同的实施方式中，用来将气体引入基材加工区域570的小孔555的数量可以约为100至5000，或者约为500至2000。所述小孔555的直径可以约为0.1-2毫米。
图5B是根据所述的实施方式，用于加工室的莲蓬头553的底视图。莲蓬头553对应于图5A所示的莲蓬头。通孔556设置成在莲蓬头553的底部具有较大的内径(ID)，在顶部具有较小的内径。小孔555基本均一地分布在莲蓬头的表面上,甚至分布在通孔556之中，与本发明所述的其它实施方式相比，所述小孔555有助于更均一的混合。
当通过莲蓬头553中的通孔556到达的等离子体流出物与从空心体积551通过小孔555到达的含硅前体合并的时候，在基材加工区域570中由底座(图中未显示)支承的基材上形成示例性的膜。虽然可以对基材加工区域570进行装配来支承等离子体用于其它的加工(例如固化)，在示例性的膜的生长过程中，没有等离子体。
可以在莲蓬头553上方的室等离子体区域520内或者在莲蓬头553下方的基材加工区域570内激发等离子体。在室等离子体区域520中存在等离子体,用来由流入的含氮-和-氢的气体产生自由基氮前体。在沉积过程中，通常在所述加工室的传导性顶部部分521和莲蓬头553之间施加射频(RF)范围的直流电压，从而在室等离子体区域520中激发等离子体。RF能量源产生13.56MHz的高RF频率，但是还会单独产生其它频率或者与13.56MHz频率组合产生其它的频率。
当基材加工区域570内的底部等离子体开启的时候，顶部等离子体可以处于低功率或无功率的状态，用来使得膜固化或者对限定基材加工区域570的内表面进行清洁。通过在莲蓬头553以及底座或者室的底部之间施加直流电压，在基材加工区域570内激发等离子体。可以在存在等离子体的情况下，将清洁气体引入所述基材加工区域570。
所述底座可以具有热交换通道，热交换流体通过所述热交换通道，用来控制基材的温度。此种构型允许对基材的温度进行冷却或加热，以保持较低的温度(从室温至大约120°C)。热交换流体可以包括乙二醇和水。还可以使用嵌入的单环路加热元件对底座的晶片支承盘(优选是铝、陶瓷或其组合)进行电阻加热，以获得较高的温度(从大约120°C至1100°C)，所述加热器元件设计成以平行的同心圆的形式形成两个完整的圆圈。所述加热器元件的外部部分可以与支承盘的外周相邻,而同心圆路径上的内部部分具有较小的半径。与加热器元件相连的金属导线通过底座的连接杆。
用系统控制器对基材加工系统进行控制。在一个示例性的实施方式中,所述系统控制器包括硬盘驱动器、软盘驱动器和处理器。所述处理器包括单板计算机(SBC),类似物和数字输入/输出面板,界面板和步进电机控制器板。CVD系统的各个部分符合Versa模块欧洲(VME)标准，限定了面板、插件箱以及连接器的尺寸和种类。所述VME标准还限定了总线结构具有16-比特数据总线和24-比特地址总线。
所述系统控制器控制CVD机器的所有活动。所述系统控制器支配系统控制软件，所述软件是储存在计算机可读介质中的计算机程序。较佳的是，所述介质是硬盘驱动器，但是所述介质也可以是其它种类的存储器。所述计算机程序包括很多组指令，用来指示时机选择、气体混合物、室压力、室温度、RF功率水平、基座位置以及具体工艺的其它参数。储存在其它存储装置(例如软盘或其它合适的驱动器)中的其它计算机程序也可以用来为系统控制器提供指令。
可以使用由系统控制器主导的计算机程序产品来实施在基材上沉积膜层叠体的过程或者用来清洁室的过程。可以使用任何常规的计算机可读编程语言编写所述计算机程序代码:例如,68000组合语言,C,C++,Pascal,Fortran等。使用常规的文件编辑器将合适的程序代码输入单个文件或者多个文件,在计算机可用介质(例如计算机的存储系统)中储存和实施。如果输入的代码文本是高等级语言,对编码进行汇编，然后将所得的汇编代码与预先汇编的微软视窗系统(Microsoft
Figure BDA00001755286200131
)图书馆路径的目标代码相关联。为了执行所述关联的汇编目标代码，系统用户调用目标代码,使得计算机系统导入存储器中的代码。然后CPU读取并执行代码，进行程序中设定的任务。
用户和控制器之间的界面是平板触敏监视器。在优选的实施方式中，使用两个监视器，一个安装在净室壁中供操作者使用，另一个安装在墙后供维护技术人员使用。所述两个监视器同时显示相同的信息，其中每次只有一个接受输入。为了选择特定的屏幕或者功能，操作者接触触敏监视器的指定区域。被接触的区域改变了其高亮度的颜色,或者显示新的菜单或屏幕,证明操作者和触敏监视器之间的通信。作为触敏监视器的替代或者补充，用户可以使用其它的装置，例如键盘、鼠标或者其它指向或通信装置与系统控制器相互交流。
在本文中，"基材"可以是其上形成有层或者没有层的支承基材。所述支承基材可以是绝缘体或者具有各种掺杂浓度和曲线的半导体，例如可以是在制造集成电路时使用的半导体基材。"氧化硅"层是含硅-氧材料的缩写，二者可以互换使用。因此，氧化硅可以包含各种浓度的其它元素态组分，例如氮、氢、碳等。在一些实施方式中,氧化硅主要由硅和氧组成。术语“前体”用来表示参与反应从而从表面除去材料或者在表面上沉积材料的任何加工气体。处于"激发态"的气体表示至少一部分气体分子处于振动激发态、解离态和/或离子化状态。气体(或前体)可以是两种或更多种气体(或前体)的组合。“自由基前体”表示参与反应用来从表面除去材料或者在表面上沉积材料的等离子体流出物(作为等离子体排出的激发态的气体)。“自由基-氮前体”表示含氮的自由基前体，“自由基-氢前体”表示含氢的自由基前体。术语"惰性气体"表示当进行蚀刻或者结合入膜中的时候不会形成化学键的任何气体。示例性的惰性气体包括稀有气体，但是还可以包括其它的气体，只要当膜中捕获痕量的所述气体时(通常)不会形成化学键即可。
在本文中使用术语"沟槽"并不表示蚀刻的几何结构具有大的水平纵横比。从表面上方观察,沟槽可以是圆形、椭圆形、多边形、矩形、或者各种其它的形状。术语“通路(via)”用来表示低纵横比的沟槽，其中可以填充了金属，也可以未填充金属，从而形成垂直的电连接。在本文中，保形层表示在表面上形成的具有与所述表面相同形状的大体均一的材料层,也即是说，所述层的表面和所述被覆盖的表面是大体平行的。本领域普通技术人员能够认识到，沉积的材料可能不会100％保形，因此术语“大体”可以包括可接受的容差。
虽然已经描述了一些实施方式，但是本领域技术人员能够认识到，可以在不背离本发明精神的前提下进行各种改良、替代结构和等价方式。另外,我们省去了对大量公知的工艺和元件的描述，以免对本发明造成不利的混淆。因此，以上描述不应看作对本发明范围的限制。
提供数值范围时，也应视作具体公开了该范围的上限和下限之间以下限单位十分之一为间隔的各中间数值，除非上下文另有明确说明。本发明还包括设定范围内任何设定数值或中间数值和该设定范围内任何其它设定数值或中间数值之间的较小范围。取决于设定范围内任何明确排除的限值，所述范围可独立地包含或排除这些较小范围的上下限，本发明也包括这些较小范围不包含限值、包含任一或两个限值的各范围。所述范围包含一个或两个限值时，排除这一个或两个限值以外的范围也包括在本发明范围内。
本文和所附权利要求书所用的单数形式“一个”、“一种”和“所述”包括复数含义，除非上下文另有明确说明。因此，例如，提到“一种工艺”包括多种这类工艺，提到“前体”包括本领域技术人员已知的一种或多种前体和其等同物，等等。
另外，在说明书和所附权利要求书中，用术语"包括"、"包含"、"含有"、"具有"和"有"来描述存在所述的特征、整数、组分或步骤,但是并不排除存在或附加一种或多种其它特征、整数、组分、步骤、动作或组的情况。

Claims (19)

1.一种在基材加工室内的无等离子体基材加工区域中的基材上形成含硅-氧的层的方法，所述方法包括：
在所述基材上沉积无碳含硅-氮-和-氢的层；以及
在含臭氧的气氛中，在固化温度条件下对所述含硅-氮-和-氢-的层进行固化，使得所述含硅-氮-和-氢的层转化为氧化硅层。
2.如权利要求1所述的方法，其特征在于，所述无碳含硅-氮-和-氢的层通过以下方式形成:
使得含氮-和/或-氢的前体流入等离子体区域，制得自由基-氮-和/或-氢前体;
在无等离子体的基材加工区域内，将无碳含硅前体与所述自由基-氮-和/或-氢前体合并;以及
在所述基材上沉积无碳含硅-氮-和-氢的层。
3.如权利要求1所述的方法，其特征在于，所述固化温度约等于或低于400℃。
4.如权利要求1所述的方法，其特征在于，所述固化温度约等于或低于200℃。
5.如权利要求1所述的方法，其特征在于，在固化操作过程中，所述固化温度从约等于或低于250℃升高到高于400℃的较高温度，从而进一步将所述无碳含硅-氮-和-氢的层转化为氧化硅层。
6.如权利要求5所述的方法，其特征在于，所述含臭氧的气氛还包含水蒸气(H2O)，同时基材处于较高的温度。
7.如权利要求1所述的方法，其特征在于，所述含氮-和/或-氢的气体包括以下物质中的至少一种：N2H2,NH3,N2和H2。
8.如权利要求1所述的方法，其特征在于，所述含氮-和/或-氢的前体含氮，所述无碳含硅前体基本不含氮。
9.如权利要求1所述的方法，其特征在于，所述含氮-和/或-氢的前体不含氮，所述无碳含硅前体含氮。
10.如权利要求1所述的方法，其特征在于，所述无碳含硅的前体包括含硅-氮的前体。
11.如权利要求1所述的方法，其特征在于，所述无碳含硅前体包括N(SiH3)3。
12.如权利要求1所述的方法，其特征在于，所述无碳含硅-氮-和-氢的层包括Si-N键和Si-H键。
13.如权利要求1所述的方法，所述方法还包括在含氧气氛中，使得基材的温度升高到约等于或高于600℃的氧退火温度。
14.如权利要求13所述的方法，其特征在于，所述含氧气氛包括选自下组的一种或多种气体：原子氧、臭氧、二氧化氮和水蒸气(H2O)。
15.如权利要求1所述的方法，其特征在于，所述基材是图案化的，包括宽度约等于或小于50纳米的沟槽。
16.如权利要求15所述的方法，其特征在于，所述沟槽中的氧化硅层是基本无孔穴的。
17.如权利要求1所述的方法，其特征在于，所述等离子体区域位于远程等离子体系统中。
18.如权利要求1所述的方法，其特征在于，所述等离子体区域是用莲蓬头与无等离子体基材加工区域隔开的基材加工室的隔离部分。
19.如权利要求1所述的方法，其特征在于，所述氧化硅主要由硅和氧组成。
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