CN103477422B - 低温氧化硅转换 - Google Patents

低温氧化硅转换 Download PDF

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CN103477422B
CN103477422B CN201280018583.XA CN201280018583A CN103477422B CN 103477422 B CN103477422 B CN 103477422B CN 201280018583 A CN201280018583 A CN 201280018583A CN 103477422 B CN103477422 B CN 103477422B
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J·梁
N·K·英格尔
S·洪
A·M·帕特尔
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Abstract

描述了一种形成氧化硅层的方法。所述方法首先通过自由基组分化学气相沉积（CVD）来沉积含硅-氮-氢（聚硅氮烷）的膜。通过在低基板温度下让聚硅氮烷膜暴露于湿气，将聚硅氮烷膜转换成氧化硅。还可把聚硅氮烷膜浸入具有氧与氢两者的液体（例如，水、过氧化氢和/或氢氧化铵）中。这些转换技术可单独或依序结合地使用。本文所述的转换技术加速了转换，产生了值得制造的膜，并且免除了对高温氧化处理的要求。臭氧处理可早于转换技术。

Description

低温氧化硅转换
相关申请的交叉引用
本申请是2011年9月20日提交的名称为“低温氧化硅转换（LOWTEMPERATURESILICONOXIDECONVERSION）”的美国专利申请第13/237,131号的PCT申请，并且涉及和要求2011年4月20日提交的名称为“低温氧化硅转换（LOWTEMPERATURESILICONOXIDECONVERSION）”的美国临时专利申请第61/477,515号的权益，所述申请全文为所有目的以引用方式并入本文中。
发明背景
自数十年前引入半导体装置以来，半导体装置几何形状已大幅缩小。现代半导体制造设备例行地制造具有45纳米（nm）、32nm和28nm的特征尺寸的装置，并且开发和使用新设备来制造甚至更小几何形状的装置。减小的特征尺寸导致装置上的结构特征空间尺寸缩小。装置上的间隙与沟槽的宽度变窄至间隙深度与宽度的深宽比变得足够高，因而难以用介电材料填充间隙。沉积的介电材料易于在间隙完全填充之前堵塞顶部，以致在间隙中间产生孔隙或裂缝。
多年来，已开发许多技术来避免介电材料堵塞间隙顶部或者“治愈”已形成的孔隙或裂缝。一种方法始于高流动性的前驱物材料，所述前驱物材料以液相形式涂抹于旋转基板表面（例如，SOG沉积技术）。这些流动性前驱物可流入和填充很小的基板间隙，而不形成孔隙或细缝。然而，一旦沉积这些高流动性材料，所述高流动性材料就硬化成固态介电材料。
在许多情况下，硬化包括热处理以自沉积材料移除碳与羟基而留下固态电介质，例如氧化硅。不幸的是，分离的碳与羟基物质通常在硬化电介质内留下孔洞，所述孔洞降低了最终材料的质量。此外，硬化电介质的体积还易收缩，以致在电介质与周围基板的界面处留下裂痕与空间。在一些情况下，硬化电介质的体积减少40%或以上。
旋涂式电介质（SOD）还用于流入图案化基板上的特征。所述材料通常从含硅、氮与氢的硅氮烷型膜转换成氧化硅。含硅、氮与氢的膜通常在高温、在含氧环境下转换成氧化硅。来自环境中的氧取代氮与氢以产生氧化硅膜。对于一些电路架构，高温暴露于氧环境会破坏下方的膜。所述考虑导致在制造工艺流程期间需要保留在“热预算”内。热预算考虑大大使SOD限制在并入下方氮化硅层的工艺流程（例如，DRAM应用），所述氮化硅层可保护下方特征不被氧化。
因此，需要新沉积工艺和材料以在结构基板上形成介电材料，而无需在含氧环境中进行高温处理。在本申请中满足了上述和其它需求。
发明内容
描述了一种形成氧化硅层的方法。所述方法首先通过自由基组分化学气相沉积（CVD）来沉积含硅-氮-氢（聚硅氮烷）的膜。通过在低基板温度下让聚硅氮烷膜暴露于湿气，将聚硅氮烷膜转换成氧化硅。还可把聚硅氮烷膜浸入具有氧与氢两者的液体（例如，水、过氧化氢和/或氢氧化铵）中。这些转换技术可单独或依序结合地使用。本文所述的转换技术加速了转换、产生了值得制造的膜，并且免除了对高温氧化处理的要求。臭氧处理可早于转换技术。
本发明实施例包括在基板上形成氧化硅层的方法。所述方法包括：形成含硅-氮-氢的层。形成含硅-氮-氢的层包括：使未激发前驱物流入远程等离子体区，以产生自由基前驱物；在无等离子体基板处理区中，结合含硅前驱物与自由基前驱物；以及在基板上沉积含硅-氮-氢的层。所述方法进一步包括：在含臭氧气氛中，固化含硅-氮-氢的层，以将含硅-氮-氢的层转换成含硅-氧的层。所述方法进一步包括让含硅-氧的层暴露于相对湿度为至少50%的潮湿气氛，以将含硅-氧的层转换成氧化硅层。
本发明实施例包括在基板上形成氧化硅层的方法。所述方法包括：形成含硅-氮-氢的层。形成含硅-氮-氢的层包括：使未激发前驱物流入远程等离子体区，以产生自由基前驱物；在无等离子体基板处理区中，结合含硅前驱物与自由基前驱物；以及在基板上沉积含硅-氮-氢的层。所述方法进一步包括：在含臭氧气氛中，固化含硅-氮-氢的层，以将含硅-氮-氢的层转换成含硅-氧的层。所述方法进一步包括：把含硅-氧的层浸入包含氧与氢的液体溶液中，以将含硅-氧的层转换成氧化硅层。
附加实施例和特征在以下的具体实施方式中部分地进行了阐述，并且所述附加实施例和特征在本领域技术人员审阅说明书之后变得显而易见或者可通过实践本发明来知晓。借助于说明书所述的工具、组合和方法，可实现和获得本发明的特征和优点。
附图说明
藉由参照说明书的其余部分和附图，可进一步了解本发明的本质和优点，其中在各个附图中相同的附图标记用于指代相似的部件。在一些情况下，子标记与附图标记有关且接在连字号后面，以表示多个类似部件之一。当引用附图标记而不指明现有子标记时，拟指代所有此类多个类似部件。
图1为图示根据本发明实施例的用于制造氧化硅膜的选定步骤的流程图。
图2为图示根据本发明实施例的用于在基板间隙中形成氧化硅膜的选定步骤的另一流程图。
图3图示根据本发明实施例的基板处理系统。
图4A图示根据本发明实施例的基板处理腔室。
图4B图示根据本发明实施例的气体分配喷洒头。
具体实施方式
描述了一种形成氧化硅层的方法。所述方法首先通过自由基组分化学气相沉积（CVD）来沉积含硅-氮-氢（聚硅氮烷）的膜。通过在低基板温度下让聚硅氮烷膜暴露于湿气，将聚硅氮烷膜转换成氧化硅。还可把聚硅氮烷膜浸入具有氧与氢两者的液体（例如，水、过氧化氢和/或氢氧化铵）中。所述转换技术可单独或依序结合地使用。本文所述的转换技术加速了转换、产生了值得制造的膜，并且免除了对高温氧化处理的要求。臭氧处理可早于转换技术。
已发现让自由基组分CVD的含硅-氮-氢的膜暴露于潮湿气氛加速氧化硅转换的完成，如由傅立叶变换红外线光谱（FTIR）确定的。当未暴露于潮湿气氛时，所述膜的性质和化学计量会随时间变化。改变膜性质使制造工艺复杂化。已发现由如FTIR确定的本质上无氮含量表征，如本文所述的让膜暴露于湿气可快速且可再现地使膜性质进入稳态。已进一步发现使用除自由基组分CVD以外的方法沉积的聚硅氮烷膜无法实现稳态氧化硅膜。所述观察结果可能因相对更空旷的网络（network）所致，所述网络通过如藉由混合自由基前驱物与含硅前驱物来沉积含硅-氮的膜而制得。空旷网络容许湿气穿透到膜内更深处。如此可扩大在基板方向上的氧化物转换。已发现在不借助相对较高温的氧气气氛处理的情况下，让硅氮烷膜暴露于湿气可产生氧化硅。避免高温氧处理预期可保留在氧化预算内，进而增进装置产量和性能。还发现让含硅-氮-氢的膜暴露于含氧与氢的液体中可在低温下使膜转换成氧化硅。
已发现依据本文所包含的方法转换成氧化硅的许多自由基组分CVD膜呈现出当基板暴露于典型的洁净室气氛时不会析出（evolve）的性质。现在将描述与形成氧化硅层的方法和系统相关的额外细节。
示例性氧化硅形成工艺
图1为图示根据本发明实施例的制造氧化硅膜的方法100中的选定步骤的流程图。方法100包括：将含硅前驱物提供至基板处理区（102）。在实施例中，含硅前驱物未经等离子体激发，因此前驱物完整无缺地进入基板处理区。接着，仅由不久要引入的自由基前驱物提供激发。在本发明的实施例中，含硅前驱物可包含一些碳，或者含硅前驱物可为无碳。含硅前驱物为例如含硅-氮的前驱物、含硅-氢的前驱物、或者含硅-氮-氢的前驱物、以及其它种类的硅前驱物。如以下详细说明的，缺碳可降低沉积膜的收缩率。除了无碳以外，含硅前驱物可为无氧。缺氧会造成由前驱物形成的含硅-氮的层中的较低浓度的硅醇（Si-OH）基。沉积膜中的过量硅醇基元（moiety）将导致孔隙度和收缩率在自沉积层移除羟基（-OH）基元的后沉积步骤期间提高。
无碳的硅前驱物的特定实例可包括硅烷胺，例如H2N(SiH3)、HN(SiH3)2与N(SiH3)3、以及其它硅烷胺。在不同实施例中，硅烷胺的流率可大于或约为200标准毫升每分钟（sccm）、大于或约为300sccm、或者大于或约为500sccm。在此给出的所有流率参照双腔室基板处理系统。单一晶圆系统需要这些流率的一半，并且其它晶圆尺寸可需要按处理面积缩放流率。这些硅烷胺可与附加气体混合，附加气体可当作载气、反应气体、或者二者。示例性附加气体包括H2、N2、NH3、He与Ar、以及其它气体。无碳的含硅前驱物的例子还可包括单独或者与其它含硅（例如，N(SiH3)3）、氢（例如，H2）和/或氮（例如，N2、NH3）的气体混合的甲硅烷（SiH4）。无碳的含硅前驱物还可包括单独或者互相结合或与前述无碳的含硅前驱物结合的二硅烷、三硅烷、甚至更高级的硅烷、以及氯化硅烷。
同样，将自由基前驱物提供至基板处理区（104）。自由基前驱物描绘在基板处理区外部的等离子体激发中由任何稳定物质（惰性或反应性）产生的等离子体流出物。自由基前驱物可为含氮自由基前驱物，所述含氮自由基前驱物在此称作氮自由基前驱物。氮自由基前驱物为含氮自由基的前驱物，含氮自由基的前驱物在基板处理区外部由更稳定的氮前驱物产生。稳定前驱物在此可称作未激发前驱物，以表示前驱物尚未穿过等离子体。可在腔室等离子体区或者在处理腔室外部的远程等离子体系统（RPS）中活化包含NH3、联氨（N2H4）和/或N2的稳定氮前驱物化合物，以形成氮自由基前驱物，接着将氮自由基前驱物输送到基板处理区中以激发含硅前驱物。在不同实施例中，稳定氮前驱物还可为包含NH3与N2、NH3与H2、NH3与N2与H2、以及N2与H2的混合物。联氨还可用来代替或结合NH3，并且用于包含N2与H2的混合物。在不同实施例中，稳定氮前驱物的流率可大于或约为300sccm、大于或约为500sccm、或者大于或约为700sccm。在腔室等离子体区中产生的氮自由基前驱物可为·N、·NH、·NH2等中的一个或多个，并且还可伴有在等离子体中形成的离子化物质。氧源还可结合远程等离子体中更稳定的氮前驱物，以使膜预先充满氧，同时降低流动性。氧源可包括O2、H2O、O3、H2O2、N2O、NO或NO2中的一个或多个。
在采用腔室等离子体区的实施例中，氮自由基前驱物在与沉积区隔开的基板处理区的区段中产生，前驱物在所述沉积区中混合和反应以在沉积的基板（例如，半导体晶圆）上沉积含硅-氮的层。氮自由基前驱物还可伴随载气，例如氢气（H2）、氮气（N2）、氦气等。在含硅-氮-氢的层生长期间以及在低温臭氧固化期间，基板处理区在此可被描述成“无等离子体”。“无等离子体”未必意味着所述区缺乏等离子体。腔室等离子体区中的等离子体边界很难界定，并且可能经由喷洒头中的孔径超出基板处理区。在感应耦合的等离子体的情况下，例如可直接在基板处理区内开始少量离子化。另外，可在基板处理区中产生低强度等离子体，而不消除形成膜的流动性本质。在产生氮自由基前驱物期间，使等离子体的离子密度比腔室等离子体区低的所有原因未脱离如本文所述的“无等离子体”的范围。
在基板处理区中，无碳的硅前驱物与氮自由基前驱物混合和反应以在沉积的基板上沉积含硅-氮-氢的膜（106）。在实施例中，可使用一些制法组合来共形地沉积所述沉积的含硅-氮-氢的膜。在其它实施例中，不像常规氮化硅（Si3N4）膜沉积技术，所述沉积的含硅-氮-氢的膜具有流动性。在形成期间具有流动性本质允许膜在固化之前流入窄的特征。
含硅-氮-氢的膜中的氮源自自由基前驱物或未激发前驱物（或者二者）。在一些实施例中，无碳的含硅前驱物实质上为无氮。然而，在其它实施例中，无碳的含硅前驱物和氮自由基前驱物两者含有氮。在第三种实施例中，自由基前驱物实质上为无氮，并且含硅-氮-氢的层的氮可由无碳的含硅前驱物供应。如此，自由基前驱物在此可称作“氮和/或氢自由基前驱物”，此意指前驱物含有氮和/或氢。类似地，流入等离子体区以形成氮和/或氢自由基前驱物的前驱物可称作含氮和/或含氢前驱物。所述命名法可应用到所述的各个实施例。在实施例中，含氮和/或含氢前驱物包含氢气（H2），而氮和/或氢自由基前驱物包含·H等。
返回图1所示的特定实例，含硅-氮-氢的膜的流动性可能起因于将氢自由基前驱物与无碳的含硅前驱物混合所引起的各种性质。这些性质可包括沉积膜中的大量氢组分和/或短链聚硅氮烷聚合物的存在。在形成所述膜期间和之后，这些短链生长和网布以形成更致密的介电材料。例如，沉积膜可具有硅氮烷型、Si-NH-Si主干（即，无碳的Si-N-H膜）。当含硅前驱物与自由基前驱物两者均为无碳时，所述沉积的含硅-氮-氢的膜实质上也为无碳。当然，“无碳”未必意味着所述膜甚至缺少微量碳。在前驱物材料中可能存在碳污染物，所述前驱物材料进入所述沉积的含硅-氮的前驱物。然而，这些碳杂质量远比可在具有碳基元的硅前驱物（例如，TEOS、TMDSO等）中发现的碳杂质量少。
在沉积含硅-氮-氢的层之后，在臭氧中固化沉积的基板。固化阶段涉及让含硅-氮-氢的层暴露于含臭氧气氛（108）。在实施例中，在基板处理区外部产生臭氧并使臭氧流入基板处理区。在本发明的不同实施例中，等离子体功率可以或可以不被施加至基板处理区，以进一步激发臭氧气氛。在实施例中，缺乏等离子体避免了产生原子氧，所述原子氧会关闭近表面的网络且阻止次表面的氧化。由于相对比较稳定的臭氧穿透敞开的硅-氮-氢的层网络，氮的减少和氧的增加不仅在表面附近发生，而且在次表面区中发生。在实施例中，随后可将等离子体施加至基板处理区，以在另一臭氧固化阶段中激发臭氧气氛。
接着，描述应用到固化操作的各种参数。沉积的基板可留在基板处理区以供固化，或者基板可传送到引入含臭氧气氛的不同腔室。在不同实施例中，在任一/两个阶段期间的基板的固化温度可低于或约为300℃、低于或约为250℃、低于或约为225℃、或者低于或约为200℃。在不同实施例中，基板的温度可高于或约为室温（25℃）、高于或约为50℃、高于或约为100℃、高于或约为125℃、或者高于或约为150℃。根据附加的所述实施例，任何上限可结合任何下限以形成附加的基板温度范围。在所述实施例中，在固化操作期间臭氧进入基板处理区的流率（只有臭氧贡献）可大于500sccm、大于1标准升每分钟（slm）、或者大于2slm。在所述实施例中，在固化操作期间的臭氧分压可大于或约为20托耳、大于或约为30托耳、大于或约为50托耳、或者大于或约为100托耳。
固化操作将含硅-氮-氢的层改性成含硅-氧的层。藉由让含硅-氧的层暴露于潮湿环境，将含硅-氧的层转换成氧化硅（操作110）。在所述实施例中，可在用以固化的相同区域中提供潮湿环境，或者可把基板移到分离的处理站。在本发明实施例中，潮湿环境的相对湿度可大于50%、大于60%、大于70%、大于75%、大于80%、或者大于85%。在实施例中，基板温度可为室温（25℃）至约100℃、约40℃至约95℃、约50℃至约90℃、约60℃至约90℃、或者约70℃至约90℃。在本发明实施例中，湿气处理的持续时间（duration）可少于2分钟、少于5分钟、少于10分钟、少于30分钟、或者少于1小时。
臭氧固化操作通常在比湿气处理高的基板温度下进行。在实施例中，由于在相同区域内准确调整这些低温有点困难，因此可在分离的腔室/站中进行固化操作和湿气处理。把本文所述的低温湿气处理包括在内将不需要高温氧气气氛退火（例如，约400℃或更高）。在本发明实施例中，固化操作结合湿气处理可完成氧化硅转换工艺。在其它实施例中，只有湿气处理用于进行转换工艺。在任一情况下，去除高温氧处理容许在不氧化下层的情况下进行转换工艺。在氧气气氛中缺少高温退火使得集成电路制造商能够保留在氧化预算内。去除这些较高温氧退火增进了集成电路装置的产量和性能。虽然本文所述的本发明已排除氧化退火，但是在实施例中，可包括高温惰性退火，以密实氧化硅膜。惰性环境中的高温退火计入热预算，但是不计入更特定的氧化预算，每一预算被确定用于特定工艺流程且与所述特定工艺流程有关。
固化操作的含臭氧气氛和湿气处理的水分含量各自提供氧，以将含硅-氮-氢的膜转换成氧化硅（SiO2）膜。利用傅立叶变换红外线光谱学（FTIR）来分析Si-O、Si-OH和Si-N键的浓度。已发现仅在臭氧固化操作之后，峰值和相关浓度随时间变化。所述膜的析出性质使制造工艺流程复杂化。在实施例中，在首先经臭氧固化且接着经湿气处理之后，FTIR峰值不会随时间发展。
现在参照图2，根据本发明实施例图示另一流程图，所述流程图示出用于在基板间隙中形成氧化硅膜的方法200中的选定步骤。基板可具有多个间隙供形成于基板上的装置部件（例如晶体管）间隔和组织。所述间隙的高度与宽度定义高度与宽度（即，H/W）的深宽比（AR），所述AR明显大于1：1（例如，5：1或以上、6：1或以上、7：1或以上、8：1或以上、9：1或以上、10：1或以上、11：1或以上、12：1或以上等）。在许多情况下，高AR因范围为约90nm至约22nm或以下（例如，小于90nm、65nm、50nm、45nm、32nm、22nm、16nm等）的小间隙宽度所致。
在基板处理区中，使含硅前驱物与自由基前驱物混合（操作204）。在基板上沉积流动性的含硅-氮-氢的层（操作206）。由于所述层具有流动性，因此所述层可填充具有高深宽比的间隙，而不在填充材料中心附近形成孔隙或细缝。例如，沉积的流动性材料不太可能在间隙完全填充之前过早地堵塞间隙顶部，以致在间隙中间留下孔隙。
接着在固化操作（208）中，固化如沉积的含硅-氮-氢的层，所述固化操作具有与在图1的操作108的描述中略述的实施例一样的实施例。以所述方式，将含硅-氮-氢的层转换成含硅-氧的层。
接着把基板传送出含臭氧气氛，并且把含硅-氧的层浸入包含氧与氢两者的液体溶液中（操作210），以完成氧化硅层转换。在本发明实施例中，由于液体溶液步骤的存在，在含氧环境中的进一步退火不是必要的。如本文所述，臭氧固化和把所得膜浸入液浴中可在基板上（包括基板间隙）形成氧化硅层（208）。如上所述，氧化硅层比起以含碳前驱物形成的类似层有较少孔洞和较少体积缩减，在热处理步骤之前所述含碳前驱物有大量碳存在所述类似层中。在许多情况下，使体积稍微适度缩小（例如，约15体积%或以下），以免后热处理步骤填充、治愈或以其它方式消除因氧化硅收缩而在间隙内形成的空间。在一些实施例中，沟槽中的氧化硅层实质上为无孔隙。
在把固化膜浸入液浴的操作期间，液浴、基板和固化膜可维持在相同温度。在实施例中，液浴可为室温（25℃）至约100℃、约40℃至约95℃、约50℃至约90℃、约60℃至约90℃、或者约70℃至约90℃。在本发明实施例中，液浴浸没的持续时间可少于2分钟、少于5分钟、少于10分钟、少于30分钟、少于1小时、少于2小时、或者少于5小时。在本发明实施例中，已发现一旦已如所述依序以臭氧固化和液浴来处理硅-氮-氢的层，就不需后续高温氧退火。发明人进一步发现在一些情况下，液浴可足以将含硅-氧的层转换成氧化硅。达成氧化硅都不需前置臭氧固化或后续高温氧退火。FTIR再次用来确定在完成基板处理之后，这种氧化硅膜不会显示随时间发展的峰高与位置。在经基板处理之后，并且当基板和膜暴露于典型洁净室气氛时，FTIR的结果实质上不变。
液浴或液体溶液包含氧与氢，且可包括水、过氧化氢或氢氧化铵中的一个或多个。在浸入操作210期间，把硅-氧膜浸入液体溶液中，并且在一些实施例中，基板可浸没在液体溶液中。在实施例中，液体溶液可为SC1或SC2浴。液体溶液可包含去离子水、至少10%的氢氧化铵和至少10%的过氧化氢。所有百分比在此按体积给出。液体溶液可包含去离子水、至少10%的氢氯酸和至少10%的过氧化氢。其它液浴可设计成具有氧与氢两者。发明人还发现当pH下降至酸性范围或上升至碱性范围时，氧化硅的转换速率提高。可在对示例性氧化硅沉积系统的描述期间引入附加参数。
示例性氧化硅沉积系统
可实现本发明实施例的沉积腔室可包括高密度等离子体化学气相沉积（HDP-CVD）腔室、等离子体增强化学气相沉积（PECVD）腔室、次常压化学气相沉积（SACVD）腔室、热化学气相沉积腔室、以及其它类型的腔室。可实现本发明实施例的CVD系统的特定实例包括CENTURAULTIMAHDP-CVD腔室/系统和PRODUCERPECVD腔室/系统，所述腔室/系统可取自美国加利福尼亚州圣克拉拉市的应用材料公司（AppliedMaterials,Inc.）。
可与本发明示例性方法一起使用的基板处理腔室的实例可包括在Lubomirsky等共同转让的美国临时专利申请第60/803,499号、2006年5月30日提交、名称为“用于电介质填隙的处理腔室（PROCESSCHAMBERFORDIELECTRICGAPFILL）”中所示和所述的基板处理腔室，所述临时专利申请为所有目的以引用方式并入本文中。附加示例性系统可包括在美国专利第6,387,207号与第6,830,624号中所示及所述的系统，所述专利还为所有目的以引用方式并入本文中。
沉积系统实施例可并入更大的制造系统来制造集成电路芯片。图3图示根据所述实施例的沉积、烘烤和固化腔室的一种此类系统300。在所述图中，一对前开式晶圆传送盒（FOUP）302供应基板（例如，直径300毫米（mm）的晶圆），所述基板由机器人手臂304接收，且基板在放入晶圆处理腔室308a-f之一之前，放到低压保持（holding）区306。第二机器人手臂310可用于将基板晶圆从保持区306传送到处理腔室308a-f以及回传。
处理腔室308a-f可包括一个或多个系统部件，用以沉积、退火、固化和/或蚀刻基板晶圆上的流动性介电膜。在一种配置下，两对处理腔室（例如，308c-d和308e-f）可用于在基板上沉积流动性介电材料，并且第三对处理腔室（例如，308a-b）可用于退火经沉积的电介质。在另一配置下，相同的两对处理腔室（例如，308c-d和308e-f）可被配置以沉积和退火基板上的流动性介电膜，而第三对腔室（例如，308a-b）可用于UV或电子束固化沉积膜。在又一配置下，所有三对腔室（例如，308a-f）可被配置以沉积和固化基板上的流动性介电膜。在再一配置下，两对处理腔室（例如，308c-d和308e-f）可用于沉积以及UV或电子束固化流动性电介质，而第三对处理腔室（例如，308a-b）可用于退火介电膜。在不同实施例中，对于与所示制造系统分离的腔室，可进行所述任何一个或多个工艺。
此外，处理腔室308a-f中的一个或多个可被配置成湿式处理腔室。这些处理腔室包括在包括水分的气氛中加热流动性介电膜。因此，系统300的实施例可包括湿式处理腔室308a-b和退火处理腔室308c-d，以对沉积的介电膜进行湿式和干式退火。
图4A为根据所述实施例的基板处理腔室400。远程等离子体系统（RPS）410可处理气体，所述气体接着行经气体入口组件411。在气体入口组件411内可见两个不同的气体供应通道。第一通道412运载气体，所述气体穿过远程等离子体系统（RPS）410，而第二通道413绕过RPS410。在所述实施例中，第一通道412可用于工艺气体，并且第二通道413可用于处理气体。盖子（或导电顶部）421和穿孔隔板（喷洒头453）被显示为在两者之间有绝缘环424，以允许相对于喷洒头453将AC电位施加至盖子421。工艺气体行经第一通道412而进入腔室等离子体区420，并且可由腔室等离子体区420中的等离子体单独或结合RPS410激发工艺气体。腔室等离子体区420和/或RPS410的组合在此称作远程等离子体系统。穿孔隔板（也称作喷洒头）453隔开腔室等离子体区420和喷洒头453下方的基板处理区470。喷洒头453容许等离子体存在于腔室等离子体区420，以免直接激发基板处理区470中的气体，同时仍然允许激发物质从腔室等离子体区420进入基板处理区470。
喷洒头453设在腔室等离子体区420与基板处理区470之间，并且喷洒头453容许腔室在等离子体区420内产生的等离子体流出物（前驱物或其它气体的激发衍生物）穿过多个穿孔456，所述穿孔456横跨板材厚度。喷洒头453还具有一个或多个中空容积451，所述中空容积451可填充有蒸汽或气体形式的前驱物（例如，含硅前驱物），并且所述前驱物经由小孔455进入基板处理区470，但是不直接进入腔室等离子体区420。在此所述实施例中，喷洒头453比穿孔456的最小直径450的长度厚。为了维持显著浓度的激发物质从腔室等离子体区420穿透至基板处理区470，可通过形成穿孔456的较大直径部分穿过喷洒头453，以限制穿孔的最小直径450的长度426。在所述实施例中，穿孔456的最小直径450的长度可与穿孔456的最小直径一样量级或更小。
在所示实施例中，喷洒头453可分配（经由穿孔456）工艺气体和/或这些工艺气体在经腔室等离子体区420中的等离子体激发之后产生的等离子体流出物，所述工艺气体含有氧、氢和/或氮。在实施例中，经由第一通道412引入RPS410和/或腔室等离子体区420的工艺气体可含有氧气（O2）、臭氧（O3）、N2O、NO、NO2、NH3、包括N2H4的NxHy、甲硅烷、二硅烷、TSA和DSA中的一种或多种。工艺气体还可包括载气，例如氦气、氩气、氮气（N2）等。第二通道413还可输送工艺气体和/或载气和/或用以自生长或如沉积的膜移除不想要的组分的膜固化气体（例如，O3）。等离子体流出物可包括工艺气体的离子化或中性衍生物，且在此还可称作氧自由基前驱物和/或氮自由基前驱物，所述前驱物与引入的工艺气体的原子成分有关。
在实施例中，穿孔456的数量可为约60至约2000个。穿孔456可具有各种形状，但是最容易制作成圆形。在所述实施例中，穿孔456的最小直径450可为约0.5mm至约20mm、或者约1mm至约6mm。在选择穿孔截面形状方面也有余地，所述穿孔截面可制作成圆锥形、圆柱形、或者两种形状的组合。在不同实施例中，用以将气体引入基板处理区470的小孔455的数量可为约100至约5000个或者约500至约2000个。小孔455的直径可为约0.1mm至约2mm。
图4B为根据所述实施例的与处理腔室一起使用的喷洒头453的底视图。喷洒头453对应于图4A所示的喷洒头。穿孔456绘示成在喷洒头453的底部有较大内径（ID），且在顶部有较小ID。小孔455实质上均匀地分布在喷洒头表面、甚至在穿孔456之间，如此有助于提供比所述其它实施例更均匀的混合。
当经由喷洒头453中的穿孔456到来的等离子体流出物结合经由源自中空容积451的小孔455到来的含硅前驱物时，在基板上形成示例性膜，所述基板由基板处理区470内的基座（未图示）支撑。虽然基板处理区470可装配以支持等离子体以供其它工艺，例如固化，但是在示例性膜生长期间，不存在等离子体。
可在喷洒头453上方的腔室等离子体区420或喷洒头453下方的基板处理区470中点燃等离子体。在腔室等离子体区420中存在等离子体，以从含氮-氢的气体的流入物产生氮自由基前驱物。在处理腔室的导电顶部（盖子421）与喷洒头453之间施加AC电压，以在沉积期间点燃腔室等离子体区420中的等离子体，所述AC电压通常处于射频（RF）范围。RF电源产生13.56兆赫（MHz）的RF高频，但是RF电源也可单独或结合13.56MHz的频率产生其它频率。
在第二固化阶段或清洁界定基板处理区470的内面期间，当基板处理区470中的底部等离子体开启时，顶部等离子体可处于低或无功率。藉由在喷洒头453与腔室的基座或底部之间施加AC电压，点燃基板处理区470中的等离子体。当等离子体存在时，可将清洁气体引入基板处理区470。
基座可具有热交换通道，热交换流体流经热交换通道，以控制基板温度。所述构造允许冷却或加热基板温度，以维持相对较低的温度（从室温至约120℃）。热交换流体可包含乙二醇和水。还可利用嵌入式单回路加热元件，电阻加热基座的晶圆支撑盘（较佳为铝、陶瓷、或者上述物质的组合物）以达到相对较高的温度（从约120℃至约1100℃），所述加热元件以平行同心圆形式配置成完整两圈。加热元件的外部可邻接支撑盘周围运作，而内部在半径较小的同心圆路径运作。加热元件的接线穿过基座主干。
基板处理系统受控于系统控制器。在示例性实施例中，系统控制器包括硬盘驱动器、软盘驱动器和处理器。处理器含有单板计算机（SBC）、模拟与数字输入/输出板、接口板和步进马达控制板。CVD系统的各种零件都符合规范板、卡笼和连接器尺寸与类型的VersaModularEuropean（VME）标准。VME标准还定义具有16位数据总线与24位地址总线的总线结构。
系统控制器控制沉积系统的所有动作。系统控制器执行系统控制软件，所述软件为储存在计算机可读介质的计算机程序。较佳地，介质为硬盘驱动器，但是介质还可为其它类型的存储器。计算机程序包括指定特定工艺的时序、混合气体、腔室压力、腔室温度、RF功率水平、晶座位置和其它参数的指令集。储存在其它存储器装置（例如，包括软盘或其它适合驱动器）的其它计算机程序还可用来指示系统控制器。
可利用由系统控制器执行的计算机程序产品来施行用于在基板上沉积膜叠层、将膜转换成氧化硅的工艺或者用于清洁腔室的工艺。计算机程序代码可以任何传统计算机可读编程语言编写：例如，68000汇编语言、C、C++、Pascal、Fortran或其它语言。适当的程序代码利用传统文字编辑器输入单一文件或多个文件，并且储存或收录在诸如计算机的存储器系统之类的计算机可用介质中。如果输入码文本为高级语言，则进行编码，并且产生的编译器代码接着于预先编译的MicrosoftWindows库例程的目标代码链接。为了执行链接的编译目标代码，系统用户调用目标代码，使计算机系统加载存储器中的代码。CPU接着读取和执行代码，以进行在程序中识别的任务。
用户与控制器之间间的界面经由平板触敏显示器。在较佳实施例中，采用两个显示器，一个显示器装设在洁净室壁中以供操作员使用，另一显示器放置在壁后方以供维修技师使用。两个显示器可同时显示相同的信息，在所述情况下一次只有一个显示器接受输入。为了选择特定画面或功能，操作员触碰触敏显示器的指定区域。触碰区域改变醒目颜色，或者显示新的菜单或画面，以确定操作员与触敏显示器之间的通信。代替触敏显示器或者除了触敏显示器以外，可使用诸如键盘、鼠标或其它点触或通信装置之类的其它装置，以允许用户与系统控制器通信。
如本文使用的，“基板”可为在所述基板上具有或不具有多个层的支撑基板。支撑基板可为绝缘体或者具有各种掺杂浓度与轮廓的半导体，并且可以是例如用于制造集成电路的类型的半导体基板。“氧化硅”层可包括低浓度的其它元素成分，例如氮、氢、碳等。在一些实施例中，氧化硅本质上由硅与氧组成。术语“前驱物”用于指代参与反应以自表面移除材料或在表面上沉积材料的任何工艺气体。处于“激发态”的气体描绘其中至少一些气体分子处于振动激发、游离和/或离子化状态的气体。气体（或前驱物）可为二种或更多种气体（或前驱物）的组合物。“自由基前驱物”用于描绘等离子体流出物（正退出等离子体的激发态的气体），所述等离子体流出物参与反应以自表面移除材料或在表面上沉积材料。“氮自由基前驱物”是含氮的自由基前驱物，并且“氢自由基前驱物”是含氢的自由基前驱物。词语“惰性气体”指当蚀刻或并入膜时不会形成化学键的任何气体。示例性惰性气体包括稀有气体，但是也可包括其它气体，只要微量（通常）陷入膜时不会形成化学键即可。
通篇所用术语“沟槽”并非暗示蚀刻的几何形状具有大的横向深宽比。从表面上方观看，沟槽可呈圆形、椭圆形、多边形、矩形、或各种其它形状。术语“通孔”用于指低深宽比沟槽，通孔可以或可不填有金属以形成纵向电连接。如在此使用的，共形层指与所述表面具有相同形状的表面上大致均匀的材料层，即所述层的表面和待覆盖的表面大致平行。本领域普通技术人员将理解沉积材料不太可能是100%共形，并且由此术语“大致”允许可接受容限。
根据上述数个实施例，本领域技术人员将理解，可使用各种修改、替换构造和等同物，而不脱离本发明的精神。此外，大量熟知的工艺和元件并未提及，以免不必要地混淆本发明。因此，以上说明不应视为限制本发明的范围。
应理解除非上下文特别指明，否则提供的数值范围到下限单位的十分之一还明确揭示介于所述范围上限与下限之间的中间值。介于论述范围内任何论述值或中间值与论述范围内的任何其它论述值或中间值之间的每一较小范围也包含在内。这些较小范围的上限与下限可独立地涵盖在所述范围内或排除在所述范围以外，并且取决于论述范围中的任何特别排除的限值，本发明还包含在较小范围中包括上限和/或下限的每一范围。当论述范围包括限值中的一个或二个时，排除那些所包括的限值中的任一个或者两个的范围也包括在内。
除非上下文清楚地指明，否则如本文和后附权利要求书使用的，单数形式“一”、“一个”和“所述”包括复数引用。由此，例如，对“一个工艺”的引用包括多个此类工艺，并且对“所述前驱物”的引用包括引用一种或多种前驱物以及本领域技术人员已知的等同物等。
同样，本说明书和以下权利要求书采用的词语“包含”、“包括”、“含有”和“含”旨在指定所述特征、整体、部件或步骤的存在，但是并不排除一个或多个其它特征、整体、部件、步骤、动作或群组的存在或添加。

Claims (11)

1.一种在基板上形成氧化硅层的方法，所述方法包含：
通过下列步骤形成含硅-氮-氢的层：
使未激发前驱物流入远程等离子体区，以产生自由基前驱物；
在无等离子体的基板处理区中，结合含硅前驱物与所述自由基前驱物；以及
在所述基板上沉积所述含硅-氮-氢的层；
在含臭氧气氛中，固化所述含硅-氮-氢的层，以将所述含硅-氮-氢的层转换成含硅-氧的层；以及
让所述含硅-氧的层暴露于相对湿度为至少50％的潮湿气氛，以将所述含硅-氧的层转换成所述氧化硅层，其中在所述暴露操作期间，所述基板温度高于或等于25℃且低于100℃。
2.如权利要求1所述的方法，其中所述潮湿气氛具有至少75％的相对湿度。
3.如权利要求1所述的方法，其中在所述固化操作期间，所述基板温度高于或等于125℃且低于或等于225℃。
4.如权利要求1所述的方法，其中让所述含硅-氧的层暴露于所述潮湿气氛持续不到5小时。
5.如权利要求1所述的方法，其中让所述含硅-氧的层暴露于所述潮湿气氛持续不到2小时。
6.如权利要求1所述的方法，其中所述氧化硅层本质上由硅与氧组成。
7.如权利要求1所述的方法，其中所述含硅-氮-氢的层在沉积期间具有流动性。
8.如权利要求1所述的方法，其中所述基板经图案化且具有沟槽，所述沟槽的宽度为50纳米或更小。
9.如权利要求1的所述方法，其中所述含硅前驱物和所述含硅-氮-氢的层各自为无碳。
10.如权利要求1的所述方法，其中所述未激发前驱物包含联氨(N2H4)、氨气(NH3)、氮气(N2)和氢气(H2)中的至少一个。
11.如权利要求1所述的方法，其中所述含硅前驱物包含N(SiH3)3。
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