CN100547732C - 通过添加碳降低氮化硅蚀刻速率的方法 - Google Patents

通过添加碳降低氮化硅蚀刻速率的方法 Download PDF

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CN100547732C
CN100547732C CNB2007101260491A CN200710126049A CN100547732C CN 100547732 C CN100547732 C CN 100547732C CN B2007101260491 A CNB2007101260491 A CN B2007101260491A CN 200710126049 A CN200710126049 A CN 200710126049A CN 100547732 C CN100547732 C CN 100547732C
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silicon nitride
process chamber
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silicon
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瑞维克·巴哈迪亚
夏立群
查德·彼得森
海彻姆·马萨德
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Abstract

本发明提供了形成掺杂碳的氮化硅硬掩膜的方法。所述氮化硅硬掩膜包括掺杂碳的氮化硅层和未掺杂的氮化硅层。本发明提供了由包含碳源化合物、硅源化合物和氮源的化合物在RF功率的存在下沉积的掺杂碳的氮化硅层。本发明还提供了对氮化硅层进行UV后处理以提供氮化硅硬掩膜的方法。所述掺杂碳的氮化硅层和经UV后处理的氮化硅层具有硬掩膜层所期望的湿法蚀刻速率和干法蚀刻速率。

Description

通过添加碳降低氮化硅蚀刻速率的方法
技术领域
本发明的实施方式一般性地涉及集成电路的制造。更具体地，本发明的实施方式涉及形成氮化硅硬掩膜的方法。
背景技术
集成电路已发展成可在单个芯片上包含数百万个晶体管、电容器和电阻器的复杂器件。芯片设计的发展一直需要更快的电路和更大的电路密度。对更快电路以及更大电路密度的需求给用于制造这样的集成电路的材料提出了相应的要求。
对更大的集成电路密度的要求同样给集成电路制造中所用的工艺序列提出了要求。例如，在使用常规光刻技术的工艺序列中，在衬底上的材料层叠层上形成能量敏感阻挡层，例如光阻挡层。将图案引入此能量敏感阻挡层。然后，使用能量敏感阻挡层作为掩膜将被引入到能量敏感阻挡层的图案转移到形成在衬底上的叠层的一个或更多个层中。可以用化学蚀刻剂将被引入能量敏感阻挡层的图案转移到材料叠层的一个或更多个层中。化学蚀刻剂被设计为对叠层的材料层的蚀刻选择性大于对能量敏感阻挡层的选择性。即，化学蚀刻剂蚀刻材料叠层的一个或更多个层的速率远大于蚀刻能量敏感阻挡层的速率。对叠层的一个或多个材料层的更快的蚀刻速率通常可以防止能量敏感阻挡层在图案转移完成之前被耗尽。
然而，对集成电路上更大的电路密度的需要使更小的图案尺寸(例如，亚微米或纳米尺寸)成为必要。随着图案尺寸减小，能量敏感阻挡层的厚度必须相应地减小以控制图案分辨率。在使用化学蚀刻剂的图案转移步骤中，这种薄阻挡层并不足以掩蔽下方的层。
在能量敏感阻挡层与下方的层之间，通常使用被称为硬掩膜的中间层以便于将图案转移到下方的层中。如同能量敏感阻挡层，硬掩膜层对用于蚀刻下方层的蚀刻剂的阻挡能力更强，从而防止下方层蚀刻完成之前的硬掩膜侵蚀。
已经开发出可用作硬掩膜的氮化硅层。通常，在高温(例如800℃)下，在炉中，通过热工艺来沉积氮化硅层。这样的高温不利于对热预算具有严格要求的工艺，例如特大规模或超大规模集成电路(VLSI或ULSI)器件的制造。
因此，需要一种在低温下沉积氮化硅层的方法，其中氮化硅层具有可使其能够用作硬掩膜层的蚀刻速率性质。
发明内容
本发明一般性地提供了形成氮化硅硬掩膜的方法。氮化硅硬掩膜可以是氮化硅层或掺杂碳的氮化硅层。
在一种实施方式中，形成掺杂碳的氮化硅硬掩膜的方法包括：将碳源化合物引入处理室；将硅源化合物引入所述处理室；将氮源引入所述处理室；在所述处理室中，使所述碳源化合物、硅源化合物和氮源在RF功率的存在下反应，以将掺杂碳的氮化硅硬掩膜沉积在衬底上。
在另一种实施方式中，形成掺杂碳的氮化硅硬掩膜的方法包括：在第一流率下将三甲基硅烷引入处理室；在第二流率下将硅烷引入所述处理室，其中所述第二流率与所述第一流率之比为约50∶1～约1∶1，例如约10∶1～约1∶1；将NH3引入所述处理室；在所述处理室中，使所述三甲基硅烷、硅烷和NH3在RF功率的存在下反应，以将掺杂碳的氮化硅硬掩膜沉积在衬底上。
在另一种实施方式中，提供了形成氮化硅硬掩膜的方法。所述方法包括：将硅源化合物引入处理室；将氮源引入所述处理室；在所述处理室中，使所述硅源化合物和氮源在RF功率的存在下反应，以将氮化硅层沉积在衬底上；对所述氮化硅层进行UV后处理，以形成氮化硅硬掩膜。通过使碳源化合物、硅源化合物和氮源在RF功率的存在下反应所沉积的掺杂碳的氮化硅层也可以被UV后处理。
附图说明
因此，参考实施例，可以详细了解本发明的上述特征，并且对于上面总结的本发明进行了更具体的描述，其中的一些实施例被示于附图中。但是，应该注意，附图仅仅示出了本发明的典型实施例，因此不应被认为是对本发明的范围的限制，因为本发明可以允许其它等效的实施例。
图1A-1D示出了本发明的一种实施方式的工艺序列的不同阶段下的衬底结构的剖面示意图；
图2示出了本发明的实施方式所提供的掺杂碳的氮化硅层的湿法蚀刻速率比；
图3示出了本发明的实施方式所提供的掺杂碳的氮化硅层的FTIR峰值比。
具体实施方式
本发明提供了沉积可用作硬掩膜的氮化硅层的方法。例如，氮化硅层可被图案化，并且形成在氮化硅层中的图案可被转移通过衬底的层。这里定义的“衬底”可以包括一个或更多个层，例如叠层。
图1A-1D示出了本发明的一种实施方式的工艺序列的实例。图1A示出了包括下层102和在层102之上的层104的衬底100。图1B示出了已被沉积在衬底100的层104上的本发明的氮化硅层106。图1C示出了已形成在氮化硅层106中并使层106被图案化的特征108。图1D示出了层106中的特征108已被转移通过层104。可以使用常规的图案化和蚀刻技术来图案化和蚀刻氮化硅层106和层104。
衬底100可以是较大结构(未示出)的一部分，所述较大部分例如是STI(浅沟槽隔离)结构、晶体管的栅极器件、DRAM器件或双镶嵌结构，因此，氮化硅层可被用作硬掩膜，对构成STI结构、栅极器件、DRAM器件或双镶嵌结构的一部分的层进行图案化。硬掩膜可在被用于图案化下方的层之后留在结构中，或者硬掩膜可在图案化完成之后被去除。
这里提供的氮化硅层包括掺杂碳的氮化硅层和不含碳的氮化硅层。氮化硅层可被沉积以得到厚度不同的层，例如厚度为约
Figure C20071012604900061
～约
Figure C20071012604900062
在一种实施方式中，通过在处理室中使碳源化合物、硅源化合物和氮源反应，将掺杂碳的氮化硅层沉积在所述处理室中的衬底上。使用等离子体增强化学气相沉积(PECVD)，在能够进行化学气相沉积(CVD)的处理室中沉积掺杂碳的氮化硅层。等离子体可以使用恒定射频(RF)功率、脉冲RF功率、高频RF功率、双频RF功率、上述的组合或其它等离子体生成技术来生成。
碳源化合物向被沉积的层提供碳，并且可以是有机硅化合物。或者，除有机硅化合物以外，碳源化合物可以是有机化合物，例如烃化合物(例如乙烯)，或者是包含碳、氮和氢的化合物。
这里所用术语“有机硅化合物”意指包含有机基团中的碳原子的含硅化合物。有机基团可以包括烷基、烯基、环己烯基和芳基及其官能衍生物。在某些实施方式中，有机硅化合物不包含氧。
有机硅化合物可以是环状的或线性的。合适的环状有机硅化合物包括具有三个或更多个硅原子的环结构。可以使用的环状有机硅化合物的例子是1，3，5-丙硅烷-2，4，6-三亚甲基，-(-SiH2CH2-)3-。
合适的线性有机硅化合物包括具有线性或分支结构的脂族有机硅化合物，其中所述线性或分支结构具有一个或更多个硅原子和一个或更多个碳原子。一些示例性的线性有机硅化合物包括：
甲基硅烷                             CH3-SiH3
二甲基硅烷                           (CH3)2-SiH2
三甲基硅烷                           (CH3)3-SiH
乙基硅烷                             CH3-CH2-SiH3
乙硅烷基甲烷                         SiH3-CH2-SiH3
二(甲基硅烷基)甲烷                   CH3-SiH2-CH2-SiH2-CH3
1，2-乙硅烷基乙烷                    SiH3-CH2-CH2-SiH3
1，2-二(甲基硅烷基)乙烷              CH3-SiH2-CH2-CH2-SiH2-CH3
2，2-乙硅烷基丙烷                    SiH3-C(CH3)2-SiH3
二乙基硅烷                          (C2H5)2-SiH2
丙基硅烷                             C3H7-SiH3
乙烯基甲基硅烷                           (CH2＝CH)-SiH2-CH3
1，1，2，2-四甲基乙硅烷                  (CH3)2-SiH-SiH-(CH3)2
六甲基乙硅烷                             (CH3)3-Si-Si-(CH3)3
1，1，2，2，3，3-六甲基丙硅烷            (CH3)2-SiH-Si(CH3)2-SiH-(CH3)2
1，1，2，2，3-五甲基丙硅烷               (CH3)2-SiH-SiH(CH3)-SiH-(CH3)2
1，3-二(甲基硅烷基)丙烷                  CH3-SiH2-(CH2)3-SiH2-CH3
1，2-二(二甲基硅烷基)乙烷                (CH3)2-SiH-(CH2)2-SiH-(CH3)2
1，3-二(二甲基硅烷基)丙烷                (CH3)2-SiH-(CH2)3-SiH-(CH3)2
硅源化合物向被沉积的层提供硅，并且可以是硅烷或四乙氧基硅烷(TEOS)。在某些实施方式中，不含碳的硅化合物是硅烷。
氮源向被沉积的层提供氮，并且可以是氨(NH3)或氮气(N2)。在某些实施方式中，氮源是氨(NH3)。
可以使用能够进行等离子体增强化学气相沉积的任何处理室来沉积这里提供的掺杂碳的氮化硅层和未掺杂的氮化硅。可以使用的化学气相沉积处理室的两个例子是
Figure C20071012604900081
SE
Figure C20071012604900082
处理室和
Figure C20071012604900083
SE硅烷处理室。这两种处理室可从美国加州Santa Clara的应用材料公司获得。美国专利No.5855681中进一步描述了一种示例性的
Figure C20071012604900084
处理室，通过引用将该文结合于此。
可以在约2sccm～约2000sccm的流率下将碳源化合物引入处理室。可以在约20sccm～约2000sccm的流率下将硅源化合物引入处理室。可以在约100sccm～约15000sccm的流率下将氮源引入处理室。可选地，在0sccm～约20000sccm的流率下将载气引入处理室。载气可以是氮气或惰性气体。选择这些流率，以使只有少量的碳被结合到沉积的氮化硅层中，得到掺杂少量碳的氮化硅层。例如，可在第一流率下将碳源化合物引入处理室，并且可在第二流率下将硅源化合物引入处理室，以使第二流率与第一流率之比为约50∶1～约1∶1，例如约10∶1～约1∶1，如约7∶1。在某些实施方式中，碳源化合物是三甲基硅烷，硅源化合物是硅烷，载气是氮。
在本文中，流率是针对具有两个分隔的处理区的300mm的处理室而言的，例如可从美国加州Santa Clara的应用材料公司获得的SE处理室。因此，每个衬底处理区的流率为进入处理室的流率的一半。
在处理室中将掺杂碳的氮化硅层沉积在衬底上的过程中，衬底通常被保持在约200℃～约700℃，优选约480℃～约600℃，例如约550℃。对于300mm的衬底，处理室中所用的RF功率水平通常为约20W～约1600W。在约0.01MHz～300MHz、优选13.56MHz的频率下提供RF功率。通常将RF功率提供给处理室中的气体分配组件或“喷淋头”电极。或者(或另外地)，RF功率可被施加于处理室中的衬底支架。可以在混合频率下，例如在约13.56MHz的高频和约350kHz的低频下，提供RF功率。RF功率可以是循环的或脉冲的，并可以是连续的或非连续的。
在沉积掺杂碳的氮化硅层的过程中，喷淋头与衬底支架的间距可为约280密耳～约1500密耳，处理室中的压力可为约1Torr～约8Torr。
图2示出了根据本发明的实施方式的使用不同量的三甲基硅烷作为有机硅化合物所沉积的掺杂碳的氮化硅层的湿法蚀刻速率比。如图2所示，随着用于沉积这些层的三甲基硅烷的流率增大，湿法蚀刻速率比降低。
掺杂碳的氮化硅层的FTIR分析(未示出)表明，由于未检测到Si-C和C-C键，因此这些层掺杂了极少量的碳。然而，如图3所示，掺杂碳的氮化硅层在Si-H键与Si-N键之比上存在可检测的差别(相对于不使用有机硅化合物而沉积的氮化硅层)。
在另一种实施方式中，通过以下方法提供氮化硅硬掩膜：在处理室中，使硅源化合物和氮源在RF功率的存在下反应，以将氮化硅层沉积在衬底上，然后对该氮化硅层进行UV后处理以形成氮化硅硬掩膜。
硅源化合物可以是硅烷或四乙氧基硅烷(TEOS)。在某些实施方式中，不含碳的硅化合物是硅烷。
氮源可以是氨(NH3)或氮气(N2)。在某些实施方式中，氮源是氨(NH3)。
可以在约20sccm～约2000sccm的流率下将硅源化合物引入处理室。可以在约10sccm～约15000sccm的流率下将氮源引入处理室。可选地，在0sccm～约20000sccm的流率下将载气引入处理室。载气可以是氮气或惰性气体。
在处理室中将掺杂碳的氮化硅层沉积在衬底上的过程中，衬底通常被保持在约200℃～约700℃，优选约480℃～约600℃，例如约550℃。对于300mm的衬底，处理室中所用的RF功率水平通常为约20W～约1600W。在约0.01MHz～300MHz、优选13.56MHz的频率下提供RF功率。通常将RF功率提供给处理室中的气体分配组件或“喷淋头”电极。或者(或另外地)，RF功率可被施加于处理室中的衬底支架。可以在混合频率下，例如在约13.56MHz的高频和约350kHz的低频下，提供RF功率。RF功率可以是循环的或脉冲的，并可以是连续的或非连续的。
在沉积氮化硅层的过程中，喷淋头与衬底支架的间距可为约280密耳～约1500密耳，处理室中的压力可为约1Torr～约8Torr。
在沉积氮化硅层之后，用UV辐射对该层进行后处理。可以使用的示例性UV后处理条件包括：约1Torr～约10Torr的处理室压力和约200℃～约500℃的衬底支架温度。在后处理过程中，使例如氦或氩的净化气体流入处理室。UV后处理进行的时间长度通常为约1分钟～约60分钟，例如30分钟。UV辐射可由任何UV源提供，例如汞微波弧光灯(例如Nordson Hg灯)、脉冲氙闪光灯和高效率UV发光二极管阵列。UV辐射可以例如具有约200nm～约400nm的波长。UV辐射可以具有单一的紫外波长或宽带的紫外波长。合适的示例性单一波长紫外源包括可提供例如172nm或222nm的单一紫外波长的激发源。合适的宽带源产生波长为约200nm～约400nm的紫外辐射。这样的紫外源可从美国的Fusion公司或美国的Nordson公司获得。可以使用由包含气体的灯所产生的具有特定波长的紫外辐射，所述气体当受电激发时在特定波长下辐射。例如，合适的紫外灯可以包含Xe气，其产生波长为172nm的紫外辐射。或者，灯可以包含具有不同的相应波长的其它气体，例如，在243nm的波长下辐射的汞灯、在140nm的波长下辐射的氘灯以及在222nm下辐射的KrCl2灯。可以使用的UV处理室和处理条件的进一步细节在共同转让的于2005年5月9日提交的美国专利申请No.11/124908中有所描述，通过引用将该文结合于此。应用材料公司的NanoCureTM处理室是可购得的用于UV后处理的处理室的例子。
尽管上面提供的UV后处理是关于对不包含碳的氮化硅层进行后处理而讨论的，但是上面提供的UV后处理也可以对本发明的特定实施方式所提供的掺杂碳的氮化硅层进行。
以下实施例阐明了本发明的实施方式。这些实施例中的衬底为300mm的衬底。在
Figure C20071012604900111
SE处理室中，将掺杂碳的氮化硅层和氮化硅层沉积在衬底上。
实施例1
在约2Torr的压力、约550℃的温度和约480密耳的间距下，将掺杂碳的氮化硅层沉积在衬底上。使用以下的处理气体和流率：三甲基硅烷，50sccm；硅烷，340sccm；氨，3200sccm；氮，4000sccm。对于掺杂碳的氮化硅层的等离子体增强沉积来说，对处理室中的喷淋头电极施加60W和频率为13.56MHz、对衬底支架施加50W和频率为350kHz的RF功率，在此RF功率的存在下，使三甲基硅烷、硅烷和氨反应。掺杂碳的氮化硅层在100∶1的稀氢氟酸(HF)具有
Figure C20071012604900112
的湿法蚀刻速率，湿法蚀刻速率比(WERR)为0.6，湿法蚀刻速率均匀度为4.5％，干法蚀刻选择比为1.1。干法蚀刻选择比是本发明的膜相对于热氮化物的过度蚀刻深度的比率。获得的其它膜性质是：晶片内厚度均匀度为1.12％，折射指数为1.984，应力为66MPa，2MV/cm下的漏电流为3.2×10-9，击穿电压为6.9MV/cm。
实施例2
在约2Torr的压力、约550℃的温度和约480密耳的间距下，将氮化硅层沉积在衬底上。使用以下的处理气体和流率：硅烷，340sccm；氨，3200sccm；氮，4000sccm。对于氮化硅层的等离子体增强沉积来说，对处理室中的喷淋头电极施加60W和频率为13.56MHz、对衬底支架施加50W和频率为350kHz的RF功率，在此RF功率的存在下，使硅烷和氨反应。氮化硅层在100∶1的稀氢氟酸(HF)具有
Figure C20071012604900113
的湿法蚀刻速率，湿法蚀刻速率均匀度为2.6％，干法蚀刻选择比为1.25。获得的其它膜性质是：晶片内厚度均匀度为0.98％，折射指数为2.0077，应力为-807MPa，2MV/cm下的漏电流为2.0×10-9，击穿电压为8.4MV/cm。
然后，使用以下工艺条件对氮化硅层进行30分钟的UV后处理：氦流率为9标准升每分钟(slm)，温度为约400℃，压力为约8Torr，间距为约800密耳。经UV处理的氮化硅层在100∶1的稀氢氟酸(HF)具有
Figure C20071012604900121
Figure C20071012604900122
的湿法蚀刻速率，湿法蚀刻速率均匀度为4.23％，干法蚀刻选择比为1.0。获得的其它膜性质是：晶圆内厚度均匀度为1.18％，折射指数为2.0069，应力为-750MPa，2MV/cm下的泄漏电流为3.0×10-9，击穿电压为7.4MV/cm。
返回实施例1，应当注意，根据本发明的实施方式，在550℃的沉积温度下，可以形成湿法蚀刻速率为
Figure C20071012604900123
的掺杂碳的氮化硅层。与对在热炉中在800℃下的热工艺(非等离子体增强)中沉积的未掺杂的氮化硅层测量的
Figure C20071012604900124
的湿法蚀刻速率相比，这是显著的改善。实施例1所得的1.1的干法蚀刻选择比与对在上述热工艺中沉积的未掺杂的氮化硅层测量的1.0的干法蚀刻选择比相当。掺杂碳的氮化硅层的漏电流与热沉积的未掺杂的氮化硅层的漏电流相似，而且发现，对掺杂碳的氮化硅层的击穿电源具有较小的影响。
实施例2表明，这里提供的UV后处理将在PECVD工艺中在RF功率的存在下沉积的未掺杂的氮化硅层的湿法蚀刻速率从
Figure C20071012604900125
改善为
Figure C20071012604900126
Figure C20071012604900127
UV后处理还将干法蚀刻选择比从处理前的1.25改善为处理后的1.00，这是对在炉中在800℃下的热工艺中沉积的未掺杂的氮化硅层所测量的干法蚀刻速率比。
因此，本发明的实施方式提供了氮化硅层，所述氮化硅层使用等离子体增强沉积工艺来沉积，并且与热沉积的氮化硅层相比具有至少相当或改善的蚀刻速率。
尽管前述针对本发明的实施方式，但是可以在不脱离本发明的基本范围的条件下设计其它实施方式，并且本发明的范围由所附权利要求确定。

Claims (20)

1.一种形成掺杂碳的氮化硅硬掩膜的方法，包括：
将碳源化合物引入处理室；
将硅源化合物引入所述处理室；以及
将氮源引入所述处理室；
在所述处理室中，使所述碳源化合物、硅源化合物和氮源在RF功率的存在下反应，以将所述掺杂碳的氮化硅硬掩膜沉积在衬底上；
其中在第一流率下将所述碳源化合物引入所述处理室，在第二流率下将所述硅源化合物引入所述处理室，并且所述第二流率与所述第一流率之比为约50∶1～约1∶1。
2.如权利要求1的方法，其中所述硅源化合物包括硅烷。
3.如权利要求2的方法，其中所述氮源为NH3。
4.如权利要求1的方法，其中所述硅源化合物为四乙氧基硅烷。
5.如权利要求1的方法，其中所述碳源化合物为三甲基硅烷。
6.如权利要求1的方法，其中所述碳源化合物为烃化合物或包含碳、氮和氢的化合物。
7.如权利要求1的方法，其中所述衬底被保持在约480℃～约600℃的温度下。
8.如权利要求1的方法，还包括将所述掺杂碳的氮化硅硬掩膜图案化，并将所述掺杂碳的氮化硅硬掩膜中的图案转移通过所述衬底的层。
9.如权利要求1的方法，其中所述第二流率与所述第一流率之比为约10∶1～约1∶1。
10.一种形成掺杂碳的氮化硅硬掩膜的方法，包括：
在第一流率下将三甲基硅烷引入处理室；
在第二流率下将硅烷引入所述处理室，其中所述第二流率与所述第一流率之比为约50∶1～约1∶1；
将NH3引入所述处理室；以及
在所述处理室中，使所述三甲基硅烷、硅烷和NH3在RF功率的存在下反应，以将所述掺杂碳的氮化硅硬掩膜沉积在衬底上。
11.如权利要求10的方法，其中所述第一流率为约2sccm～约2000sccm，所述第二流率为约20sccm～约2000sccm，并且在约100sccm～约15000sccm的流率下将所述NH3引入所述处理室。
12.如权利要求10的方法，其中提供的所述RF功率的功率水平为约20W～约1600W。
13.如权利要求10的方法，其中所述衬底被保持在约480℃～约600℃的温度下。
14.如权利要求10的方法，还包括将所述掺杂碳的氮化硅硬掩膜图案化，并将所述掺杂碳的氮化硅硬掩膜中的图案转移通过所述衬底的层。
15.一种形成氮化硅硬掩膜的方法，包括：
将硅源化合物引入处理室；
将氮源引入所述处理室；
在所述处理室中，使所述硅源化合物和氮源在RF功率的存在下反应，以将氮化硅层沉积在衬底上；以及
通过对所述氮化硅层进行紫外线后处理以形成所述氮化硅硬掩膜，降低所述氮化硅层的湿法蚀刻速率。
16.如权利要求15的方法，其中所述硅源化合物为硅烷和四乙氧基硅烷，所述氮源为NH3。
17.如权利要求15的方法，其中所述衬底被保持在约480℃～约600℃的温度下。
18.如权利要求15的方法，其中氮化硅层被紫外线后处理约1分钟～约60分钟。
19.如权利要求15的方法，还包括将有机硅化合物引入处理室，并将所述有机硅化合物与所述硅源化合物和氮源反应。
20.如权利要求15的方法，还包括将所述氮化硅硬掩膜图案化，并将所述氮化硅硬掩膜中的图案转移通过所述衬底的层。
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US7951730B2 (en) 2011-05-31
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