CN111048400B - 通过循环cvd形成保形碳化硅膜的方法 - Google Patents

通过循环cvd形成保形碳化硅膜的方法 Download PDF

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CN111048400B
CN111048400B CN201910934196.4A CN201910934196A CN111048400B CN 111048400 B CN111048400 B CN 111048400B CN 201910934196 A CN201910934196 A CN 201910934196A CN 111048400 B CN111048400 B CN 111048400B
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gas
precursor
silicon carbide
film
etch
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CN111048400A (zh
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深泽笃毅
财津优
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ASM IP Holding BV
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Abstract

本申请提供了一种通过循环CVD形成保形碳化硅膜的方法，具体涉及一种在具有凹部图案的衬底上形成如在633nm下测量反射率为2.3或更高的碳化硅膜的方法，其包括：(i)以脉冲形式向其中放置衬底的反应空间供给有机硅烷前体，所述前体具有式RSiH3，其中R为包含至少一个不饱和键的含烃部分；(ii)向反应空间连续供给等离子体发生气体，所述等离子体发生气体选自惰性气体和氢化物气体；(iii)向反应空间连续施加RF功率以产生激发前体的等离子体；和(iv)重复步骤(i)至(iii)，由此在衬底上形成碳化硅膜，如在633nm下测量，所述碳化硅膜具有2.3或更高的反射率。

Description

通过循环CVD形成保形碳化硅膜的方法
技术领域
本发明总的涉及通过化学气相沉积(CVD)、特别是循环CVD形成保形碳化硅膜的方法。
背景技术
在用于例如制造集成电路层的半导体制造工艺中，SiC膜常因其优异的性质如高耐湿蚀刻性而被使用。当在具有凹部图案的图案化衬底上沉积SiC膜时，常常需要膜具有高保形性。为了沉积保形SiC膜，采用等离子体或热能的原子层沉积(ALD)可以是候选的沉积方法，因为ALD已知是沉积保形膜的一种工艺。然而，ALD的原理基于的是衬底上前体分子的化学吸附，并且由于用来沉积SiC膜的前体含有碳原子，而碳已知是会干扰分子的化学吸附的元素，故难以形成三维受控的SiC膜，其中常常在膜基质中发展出仅部分形成的骨架。虽然可通过使用前体的热分解的聚合反应来形成SiC膜，但需要高温，因此，该工艺不能应用于需要低温的工艺，如使用光刻胶等的那些。此外，虽然可通过组合沉积和蚀刻来形成保形SiC膜，但观察到加载效应，这导致图案化的可控性问题。相应地，需要形成高度保形且均匀的SiC膜。
在本公开中，取决于工艺配方，SiC膜不仅包括SiC膜，还包括SiCO膜、SiCN膜、SiCON膜等，其中除非另有说明，否则膜名称是以非化学计量方式仅指示膜类型的缩写。
对与相关技术有关的问题和解决方案的任何论述都已经仅出于向本发明提供背景的目的而包括于本公开中，并且不应被视为承认所述论述中的任一项或全部在创作本发明时都是已知的。
发明内容
在一些实施方案中，为了沉积保形SiC膜，使用弱自由基来产生初级聚合反应，由此使得能够在具有凹部图案的衬底上沉积具有高保形性的SiC膜，同时保持低的工艺温度。在一些实施方案中，保形膜是指具有80％至100％(通常约90％或更高)的保形性的膜，其中“保形性”通过比较在凹部的侧壁上或底部上的某些点(通常为横截面视图中的中间点)处沉积的膜厚度与就在凹部外的平坦表面上沉积的膜厚度来确定。
在一些实施方案中，对于其分子中所含的每一个硅原子，含硅前体含有三个Si-H键和一个具有双键或三键的烃基团。在上文中，当前体在其分子中含有两个或更多个硅原子时，Si-H键的数目和烃基团的数目将随其分子中硅原子的数目而成比例地变为两倍或更多倍。相应地，可沉积具有高反射率(RI)的SiC膜。
在一些实施方案中，对于300mm的晶片，在0℃至500℃的温度和10W至500W的RF功率下进行聚合反应。在本公开中，对于300mm晶片的任何指示的RF功率可被转换为W/cm2(每单位面积晶片的瓦特数)，其可应用于具有不同直径如200mm或450mm的晶片。
在一些实施方案中，等离子体气氛中产生聚合所需的气体为选自惰性气体和氢化物气体的单一气体或者两种或更多种气体的混合物。氢化物气体为通常不含硅或不含金属元素(但可含有碳)的供氢气体，因为氢化物气体用于回蚀膜以调节膜的拓扑结构，而不用于沉积膜。
在一些实施方案中，为了改善SiC膜的台阶覆盖率，除了沉积步骤外，还使用用氢化物气体或含有氢化物气体的气体生成的等离子体来进行等离子体回蚀步骤。
出于概述本发明的各方面和所实现的优于相关技术的优势的目的，在本公开中描述本发明的某些目的和优势。当然，应理解，未必所有这些目标或优点都可以根据本发明的任何特定实施例来实现。因此，举例来说，本领域技术人员将认识到，本发明可以按照实现或优化如本文所传授的一个优点或一组优点的方式实施或进行，而不必实现如本文中可能传授或表明的其它目标或优点。
本发明的另外方面、特征和优势将从之后的详细描述变得显而易见。
附图说明
现将参照优选实施方案的附图来描述本发明的这些和其他特征，这些优选实施方案意图说明而非限制本发明。各图出于说明性目的而被大大简化并且未必按比例。
图1A为本发明的实施方案中可用的用来沉积电介质膜的气体脉冲等离子体增强CVD(PECVD)装置的示意图。
图1B示意了本发明的实施方案中可用的使用流通系统(FPS)的前体供给系统的示意图。
图2至6分别示出了，根据本发明的实施方案，一个循环(初级循环)中气体脉冲PECVD的示意性工艺序列与一个循环(二级循环)中等离子体回蚀的示意性工艺序列的组合，其中灰色单元表示开启状态(较暗的灰色表示较高的强度)而白色单元表示断开状态，并且每列的宽度不表示每个工艺的持续时间。
图7为流程图，示意了根据本发明的实施方案的膜形成步骤。
具体实施方式
在本公开中，取决于上下文，“气体”可包括气化固体和/或液体并可由单一气体或气体的混合物构成。同样，取决于上下文，冠词“一”是指一个物种或包括多个物种的属。在本公开中，通过喷头引入反应室中的工艺气体可以包含含硅前体和添加剂气体、主要由其组成或由其组成。添加剂气体可包括等离子体发生气体(例如，稀有气体)和回蚀气体(例如，氢化物气体)，当向添加剂气体施加RF功率时，其将被激发或激活。惰性气体可作为载气和/或稀释气体进给到反应室。在一些实施方案中，不使用用于氧化、氮化或碳化前体的反应气体，或者在其他实施方案中，使用用于氧化、氮化或碳化前体的反应气体来对SiC膜掺杂O、N或C。此外，在一些实施方案中，不使用反应气体，而是仅使用稀有气体(作为载气和/或稀释气体)作为添加剂气体。在一些实施方案中，仅使用稀有气体和氢化物气体作为添加剂气体。前体和添加剂气体可以混合气体引入到反应空间或分别引入到反应空间。可利用载气如稀有气体引入前体。除工艺气体外的气体，即在不穿过喷头的情况下引入的气体，可用于例如密封反应空间，这包含如稀有气体的密封气体。在一些实施例中，术语“前体”一般是指参与产生另一化合物的化学反应的化合物，并且尤其是指构成膜基质或膜的主要构架的化合物，而术语“反应物”是指不为前体的活化前体、使前体改性或催化前体反应的化合物，其中当施加RF功率时反应物可向膜基质提供元素(如N、C)并且变成膜基质的一部分。术语“惰性气体”是指当施加RF功率时激发前体的气体，但不同于反应物，其不变成膜基质的一部分。
在一些实施方案中，“膜”是指在垂直于厚度方向的方向上连续延伸的基本上无小孔的覆盖整个目标或相关表面的层，或仅仅是指覆盖目标或相关表面的层。在一些实施例中，“层”是指在表面上形成的具有某一厚度的结构，或膜或非膜结构的同义词。膜或层可由具有某些特征的离散单个膜或层构成或由多个膜或层构成，并且相邻膜或层之间的边界可以透明或可以不透明，并且可基于物理、化学和/或任何其它特征、形成工艺或序列和/或相邻膜或层的功能或目的而建立。此外，在本公开中，由于可工作范围可基于常规工作而确定，因此变量的任何两个数字可构成变量的可工作范围，且所指示的任何范围可包括或排除端点。另外，所指示的变量的任何值(不论其是否用“约”指示)可指精确值或近似值并且包含等同物，并且在一些实施例中，可指平均值、中值、代表值、大部分值等。此外，在本公开中，在一些实施例中，术语“由……构成”和“具有”独立地指“典型地或广泛地包含”、“包含”、“基本上由……组成”或“由……组成”。在本公开中，在一些实施例中，任何所定义的含义未必排除普通和惯用含义。
在本公开中，当未指定条件和/或结构时，本领域的技术人员可以根据本公开，按照常规实验容易地提供此类条件和/或结构。
在所有的公开实施方案中，实施方案中所用的任何要素可出于既定目的而用与其等同的任何要素替换，包括本文中明确、必须或本质上公开的那些要素。此外，本发明可同等地适用于设备和方法。
将参照优选实施方案来阐述实施方案。然而，本发明不限于所述优选实施方案。
在一些实施方案中，在具有凹部图案的衬底上形成如在633nm下测量反射率为2.3或更高的碳化硅膜的方法包括步骤：(i)以脉冲形式向其中放置衬底的反应空间供给有机硅烷前体，所述前体具有式RSiH3，其中R为包含至少一个不饱和键的含烃部分；(ii)向反应空间连续供给等离子体发生气体，所述等离子体发生气体选自惰性气体和氢化物气体；(iii)向反应空间连续施加RF功率以产生激发前体的等离子体；和(iv)重复步骤(i)至(iii)，由此在衬底上形成碳化硅膜，如在633nm下测量，所述碳化硅膜具有2.3或更高的反射率(RI)(例如，2.3至2.9，优选2.5至2.8)。当膜的RI在此范围内时，可改善膜的回蚀可控性，因此，通过将膜暴露于例如氢等离子体，膜的平坦部分(即，沉积在衬底的顶表面上的部分和/或沉积在凹部的底部处的部分)可易于回蚀以改善膜的保形性或台阶覆盖率。通常，RI越高，则被氢等离子体或Ar等离子体回蚀的膜越多。此外，具有较高RI的膜往往含有更多的硅原子，而具有较低RI的膜往往含有更多的碳原子。表示上述RI的RI值可以是在平坦部分中测量的值。
当使用具有式RSH3的前体时，其中R为包含至少一个不饱和键、优选地双键或三键的含烃部分，由于前体具有相对较少的反应性基团和每个硅较多的Si-H键，故前体的反应性变高，即，即使在暴露于低能等离子体(低等离子体功率)时仍表现出高反应性。结果，不仅可改善保形性或台阶覆盖率，而且可改善图案加载性质。
在上文中，步骤(i)是间歇性的，而步骤(ii)和(iii)是连续的，因此，该技术可被称为“气体脉冲等离子体CVD”。
在本公开中，沟槽、通孔和任何其他凹部被称为“凹部”。在一些实施方案中，图案由凹部构成。在一些实施方案中，凹部具有10至50nm(通常15至30nm)的宽度、30至200nm(通常50至150nm)的深度和3至20(通常3至10)的纵横比。
在构成沉积步骤的步骤(i)至(iv)中，通过供给相对少量的前体(例如，每分钟0.001g至0.1g)，所述前体暴露于惰性气体的等离子体或惰性气体和氢的等离子体，其中发生由惰性气体等离子体的溅射或由氢等离子体的蚀刻，从而调节沉积在衬底顶表面上的膜的平坦部分的厚度以控制膜的拓扑结构，可沉积具有相对良好的台阶覆盖率的膜。应指出，氢化物气体用于回蚀效应，而不被引入到膜中(膜的组成不变)。
在一些实施方案中，有机硅烷前体为单乙酰基硅烷、单乙烯基硅烷或苯基硅烷。
在一些实施方案中，在步骤(i)中，有机硅烷前体与载气一起供给，其中所述载气为惰性气体。
在一些实施方案中，在步骤(i)中，连续供给所述载气。
在一些实施方案中，在步骤(ii)中，等离子体发生气体为选自稀有气体和氮气的惰性气体。
在一些实施方案中，等离子体发生气体还含有氢化物气体。
在一些实施方案中，氢化物气体为氢气。
在一些实施方案中，步骤(i)和步骤(iv)在0℃至500℃的工艺温度下进行。
在一些实施方案中，工艺温度为100℃或更低。当工艺温度为100℃或更低(例如，75℃或更低)时，在其下前体组分在吸附于表面上时发生聚合，所述组分有时形成可流动的液体材料而不是形成本体膜。在此情况下，可流动的液体材料可利用其表面张力填充沟槽或其他凹部而用作填隙物。
在一些实施方案中，所述方法在步骤(i)至步骤(iv)之后还包括步骤：(v)供给回蚀气体以回蚀在步骤(iv)中沉积的碳化硅的平坦部分而不向反应空间供给所述前体或任何其他前体；和(vi)在步骤(v)中供给回蚀气体的同时，向反应空间施加RF功率，从而回蚀沉积在衬底的顶表面和凹部图案的底部上的碳化硅膜的平坦部分。当沉积的膜的保形性或拓扑结构不令人满意时，可根据需要进行构成回蚀步骤的步骤(v)和(vi)。通常，当进行回蚀步骤时，在进行回蚀步骤之前吹扫反应空间，使得在反应空间中基本上不存在前体或者与前体缔合或衍生自前体的组分。在回蚀步骤中，没有沉积膜。在一些实施方案中，回蚀步骤在每几个到几百个沉积步骤循环之后进行一次，以便可调节膜的拓扑结构，其中所述沉积步骤和回蚀步骤构成膜形成步骤的循环，可重复该循环直到可取得膜的所需拓扑结构。
在一些实施方案中，回蚀气体为选自惰性气体和氢化物气体的至少一种气体。
在一些实施方案中，回蚀气体由稀有气体和氢气构成。
在一些实施方案中，在整个步骤(i)至步骤(vi)中连续供给回蚀气体。
在一些实施方案中，步骤(i)至(vi)构成一个循环并重复直至获得所需厚度的碳化硅膜。
在一些实施方案中，所述方法在步骤(iv)中重复步骤(i)至(iii)之后还包括步骤：(v’)在不存在所述前体或任何其他前体的情况下向反应空间供给惰性气体(不供给氢化物气体)而不施加RF功率；和(vi’)在向反应空间连续供给惰性气体(不供给氢化物气体)的同时，向反应空间施加RF功率，从而进一步回蚀碳化硅膜的平坦部分。步骤(v)和步骤(v’)之间的差异及步骤(vi)和步骤(vi”)之间的差异在于在步骤(v’)和(vi”)中不存在氢化物气体。如果膜的所需拓扑结构不需要在沉积步骤后进行大的调节，则可代替步骤(v)和(vi)进行步骤(v”)和(vi”)。
在一些实施方案中，在整个步骤(i)至(vi)中连续供给惰性气体，其中所述惰性气体在步骤(i)和(ii)中用作载气和稀释气体并在步骤(v’)和(vi’)中用作回蚀气体的至少一部分。
实施方案将结合附图中示意的实施方案来说明。然而，本发明不限于此。
图2至6分别示出了，根据本发明的实施方案，一个循环(初级循环)中气体脉冲PECVD的示意性工艺序列与一个循环(二级循环)中等离子体回蚀的示意性工艺序列的组合，其中灰色单元表示开启状态(较暗的灰色表示较高的强度)而白色单元表示断开状态，并且每列的宽度不表示每个工艺的持续时间。图2至6中示出的实施方案为示例性实施方案，本发明不限于此。
图2至6中示意的工艺序列由沉积步骤和进行以调节所沉积膜的拓扑结构和厚度的回蚀步骤组成，因此，如果沉积步骤提供了所需拓扑结构/厚度的沉积膜，则不进行回蚀步骤。在沉积步骤中，在“沉积”中间歇地或以脉冲供给前体，而在“沉积”和“处理1”中连续地向反应空间施加RF功率，其中“沉积”和“处理1”构成沉积步骤的一个循环。所述循环可重复数次到数百次，直至获得所需厚度的膜。在“处理1”中，由于没有前体被供给到反应空间，故没有膜沉积。在整个沉积步骤中，连续地向反应空间供给惰性气体作为等离子体发生气体。在图2、3和6中示意的工艺序列中，在沉积步骤中，连续地向反应空间供给氢化物气体，而在图4和5中示意的工艺序列中，不供给氢化物气体。当例如沉积在其中形成沟槽的顶表面上的膜的一部分的厚度在拓扑上不合需要地大于沉积在沟槽的侧壁上的膜的一部分的厚度时，使用氢化物气体，其中所述氢化物气体用作回蚀气体，并且氢气自由基可比沉积在侧壁上的膜部分更多地蚀刻沉积在顶表面上的膜部分，从而调节膜的拓扑结构。如果拓扑调节不够，则在沉积步骤重复数次到数百次之后进行回蚀步骤。
在图2至6中示意的工艺序列中，回蚀步骤包括“气流”和“处理2”，在“气流”中吹扫反应空间而不施加RF功率以从反应空间去除前体和与前体缔合或衍生自前体的任何其他组分，在“处理2”中向反应空间施加RF功率，其中连续地向反应空间供给惰性气体作为吹扫气体和等离子体发生气体。由RF功率产生的惰性气体等离子体通过溅射效应回蚀沉积在顶表面上的膜部分。在图2、5和6中示意的工艺序列中，在回蚀步骤中，连续地向反应空间供给氢化物气体，而在图3和4中示意的工艺序列中，不供给氢化物气体。当例如沉积在其中形成沟槽的顶表面上的膜部分的厚度在拓扑上不合需要地大于沉积在沟槽的侧壁上的膜部分的厚度时，使用氢化物气体，其中所述氢化物气体用作回蚀气体，并且氢气自由基可比沉积在侧壁上的膜部分更多地蚀刻沉积在顶表面上的膜部分，从而调节膜的拓扑结构。
图6中示意的工艺序列与图2中示意的工艺序列在“处理1”和“处理2”中的RF功率强度方面不同，其中图6中示意的工艺序列在“处理1”和“处理2”中使用比图2中的那些或比图6中的“沉积”中高的RF功率(例如，高1.1倍至3倍或高1.5倍至2.5倍)，使得表现出更多的回蚀效果(在其他序列中，RF功率在整个膜形成工艺中是恒定的)。
重复沉积步骤和回蚀步骤，直至可获得所述拓扑结构/厚度的膜。图7为流程图，示意了根据本发明的实施方案的膜形成步骤。在一些实施方案中，取决于预期目的和应用，沉积膜的厚度为5nm至100nm，通常8nm至30nm。
如前所述，该方法为气体脉冲PECVD方法，其中前体的聚合反应在反应空间中于气相中进行，而不是如在PEALD方法中那样只在衬底的表面上进行。在气体脉冲PECVD中，气体供给如在PEALD中那样脉冲的原因不是像在PEALD中那样自限制前体的化学吸附，然后与受激发的反应气体进行表面反应来沉积膜，而是在不供给前体的同时通过等离子体回蚀沉积膜来调节膜的拓扑结构。
在一些实施方案中，沉积步骤的“沉积”和“处理1”及回蚀步骤的“气流”和“处理2”可在下表1中示出的条件下进行。
表1(数值为近似值)
Figure BDA0002221170830000081
在本公开中，对于300mm晶片的任何指示的RF功率可被转换为W/cm2(每单位面积晶片的瓦特数)，其可应用于具有不同直径如200mm或450mm的晶片。
在本公开中描述的工艺序列中，可使用连续供给的载气以脉冲形式供给前体。这可以使用流通系统(FPS)实现，其中载气管线具备具有前体储存器(瓶)的绕道管线，并且主管线和绕道管线经切换，其中当打算仅将载气馈送到反应室时，关闭绕道管线，而当打算将载气和前驱气体馈送到反应室时，关闭主管线，并且载气流过绕道管线并且与前驱气体一起从瓶中流出。通过这种方式，运载气体可以连续流入反应室中，并且可以通过切换主管线和绕道管线以脉冲方式运载前体气体。图1B示出了根据本发明一个实施例的使用流通系统(FPS)的前体供应系统(黑色阀指示阀是关闭的)。如图1B中的(a)中所示，当将前体馈送到反应室(未显示)时，首先，载气诸如Ar(或He)流过具有阀b和c的气体管线，并且接着进入瓶(储存器)30中。载气从瓶30中流出，同时运载量对应于瓶30内部的蒸气压的前体气体，并且流过具有阀f和e的气体管线，并且接着与前体一起馈送到反应室。在上文中，阀a和d是关闭的。当仅将载气(稀有气体)馈送到反应室时，如图1B中的(b)中所示，载气流过具有阀a的气体管线，同时绕过瓶30。在上文中，阀b、c、d、e和f是关闭的。
前体可借助载气提供。用于沉积的等离子体可原位生成，例如，在整个沉积循环中连续流动的惰性气体气氛中。在其他实施方案中，可远程生成等离子体并提供给反应室。
工艺循环可使用任何合适的装置进行，包括例如图1A中示意的装置。图1A为气体脉冲PECVD装置的示意图，该装置宜与编程为进行下文所述序列的控制器结合，可用于本发明的一些实施方案中。在该图中，通过提供一对并联并且在反应室3的内部11(反应区)中彼此面对面的导电平板电极4、2，将HRF功率(13.56MHz或27MHz)20施加到一侧，并且使另一侧12电接地，在电极之间激发等离子体。在下部平台2(下部电极)中提供温度调节器，并且使其上所放置的衬底1的温度在给定温度下保持恒定。上部电极4同样充当喷淋板，并且将反应气体(和稀有气体)和前体气体分别通过气体管线21和气体管线22引入到反应室3中，并且通过喷淋板4。另外，在反应室3中，提供具有排气管线7的环形管13，通过所述排气管线排出反应室3的内部11中的气体。另外，通过气体管线23将稀释气体引入到反应室3中。此外，安置在反应室3下方的转移室5设置有密封气体管线24以将密封气体经由转移室5的内部16(转移区)引入到反应室3的内部11中，在所述转移室中提供用于隔离反应区与转移区的隔离板14(本图中省略闸阀，薄片通过所述闸阀转移到转移室5中或从所述转移室转移)。传送室还具备排气管线6。在一些实施例中，在同一反应空间中进行多元素膜的沉积和表面处理，使得所有步骤都可以连续地进行而不将衬底暴露于空气或其它含氧气氛中。在一些实施例中，远程等离子体单元可以用于激发气体。
在一些实施方案中，在图1A中所描绘的装置中，图1B中示意的切换非活性气体的流量与前体气体的流量的系统(在前面描述)可用于引入脉冲形式的前体气体而基本上不使反应室的压力波动。
在一些实施方案中，可使用双室反应器(用于加工彼此靠近设置的晶片的两个部分或隔室)，其中反应气体和稀有气体可通过共享管线供给而前体气体通过未共享管线供给。
熟练技术人员应认识，所述装置包括一个或多个编程或以其他方式配置为使得沉积和本文其他地方描述的反应器清洁工艺能够进行的控制器(未示出)。本领域的技术人员将了解，控制器与各种电源、加热系统、泵、机器人装置和反应器的气体流量控制器或阀连通。
参考以下工作实施例来进一步解释本发明。然而，所述实例并不打算限制本发明。在未指定条件和/或结构的实施例中，鉴于本公开，本领域技术人员可容易地按照常规实验提供此类条件和/或结构。另外，在一些实施例中，可以将具体实例中应用的数值修改至少±50％的范围，并且所述数值是近似值。
实施例
在其中载气(Ar)流率为2slm、工艺压力为400Pa、温度为350℃、RF功率为100W、“沉积”(参见图2-6)的持续时间为0.1秒、“处理1”(参见图2-6)的持续时间为1秒且沉积循环数为80的一般条件下使用下表2中示出的特定条件(在不进行回蚀步骤的情况下进行沉积步骤)和图1A中示意的气体脉冲PECVD装置及图1B中示意的气体供给系统(FPS)在具有纵横比为约3、开口宽度为约50nm的图案化表面的300mm衬底上形成碳化硅膜。膜(沉积在顶表面上)的厚度为10nm以评价膜性质。
表2(数值为近似值)
Figure BDA0002221170830000111
评价膜的性质，结果示于下表3中。
表3(数值为近似值)
Figure BDA0002221170830000112
Figure BDA0002221170830000121
在上文中，术语“侧面覆盖率”是指沉积在沟槽侧壁上的膜的厚度与沉积在衬底顶表面上的膜的厚度之比(％)。术语“图案加载”是指在其中沟槽的密度高的密集区域中沉积在沟槽侧壁上的膜的厚度与在其中沟槽的密度低的隔离区域中沉积在沟槽侧壁上的膜的厚度之比(％)。术语“TOX的100:1DHF湿蚀刻速率比”是指当在室温下于稀HF溶液(1％)中浸没一分钟时沉积在衬底的顶表面上的膜的湿蚀刻速率与在相同的湿蚀刻条件下热氧化物膜的湿蚀刻速率之比。术语“GPC(nm/循环)”是指每个循环沉积在衬底的顶表面上的膜的生长速率。术语“RI@633nm”是指沉积在衬底的顶表面上的膜的反射率(在633nm的波长下)。
如表3中所示，当在实施例1至实施例5中的每一个中使用具有式RSiH3的前体(其中R为包含至少一个不饱和键的含烃部分)来通过气体脉冲PECVD沉积碳化硅膜时，膜都具有2.3或更高的RI，并且膜的所有性质(侧面覆盖率、图案加载和耐湿蚀刻性)都优异。相比之下，当在比较例1和比较例2中的每一个中使用非上述前体的前体来通过气体脉冲PECVD沉积碳化硅膜时，膜都具有小于2.3的RI，并且总体性质不令人满意。
本领域技术人员应理解，可作许多和各种修改而不偏离本发明的精神。因此，应清楚地理解，本发明的形式仅是示意性的，而非意在限制本发明的范围。

Claims (14)

1.一种在具有凹部图案的衬底上形成如在633nm下测量反射率为2.3或更高的碳化硅膜的方法，所述方法包括步骤：
(i)以脉冲形式向其中放置所述衬底的反应空间供给有机硅烷前体，所述前体具有式RSiH3，其中R为包含至少一个不饱和键的含烃部分，前提是该前体不是苯基硅烷；
(ii)向所述反应空间连续供给不含氢化物气体的等离子体发生气体，所述等离子体发生气体是惰性气体；
(iii)向所述反应空间连续施加RF功率以产生激发所述前体的等离子体；和
(iv)重复步骤(i)至(iii)，由此在所述衬底上形成碳化硅膜，如在633nm下测量，所述碳化硅膜具有2.3或更高的反射率。
2.根据权利要求1所述的方法，其中所述有机硅烷前体为单乙酰基硅烷或单乙烯基硅烷。
3.根据权利要求1所述的方法，其中在步骤(i)中，所述有机硅烷前体与载气一起供给，其中所述载气为惰性气体。
4.根据权利要求3所述的方法，其中在步骤(i)中，连续供给所述载气。
5.根据权利要求1所述的方法，其中在步骤(ii)中，所述等离子体发生气体为选自稀有气体和氮气的惰性气体。
6.根据权利要求1所述的方法，其中步骤(i)和步骤(iv)在0℃至500℃的工艺温度下进行。
7.根据权利要求6所述的方法，其中所述工艺温度为100℃或更低。
8.根据权利要求1所述的方法，所述方法在由步骤(i)至步骤(iv)构成的沉积循环完成之后还包括作为沉积后处理的步骤：
(v)在不向所述反应空间供给所述前体的情况下供给回蚀气体以回蚀步骤(iv)中沉积的所述碳化硅的平坦部分；和
(vi)在步骤(v)中供给所述回蚀气体的同时，向所述反应空间施加RF功率，由此回蚀沉积在所述衬底的顶表面和所述凹部图案的底部上的所述碳化硅膜的平坦部分。
9.根据权利要求8所述的方法，其中所述回蚀气体为选自惰性气体和氢化物气体的至少一种气体。
10.根据权利要求9所述的方法，其中所述回蚀气体由稀有气体和氢气构成。
11.根据权利要求8所述的方法，其中在整个步骤(i)至步骤(vi)中连续供给所述回蚀气体。
12.根据权利要求8所述的方法，其中步骤(i)至(vi)构成一个循环并且重复直至获得所需厚度的所述碳化硅膜。
13.根据权利要求12所述的方法，所述方法在步骤(iv)中重复步骤(i)至(iii)之后还包括：
(v’)在不施加RF功率的情况下向所述反应空间供给惰性气体；和
(vi’)在向所述反应空间连续供给所述惰性气体的同时，向所述反应空间施加RF功率，从而进一步回蚀所述碳化硅膜的所述平坦部分。
14.根据权利要求13所述的方法，其中在整个步骤(i)至(vi)中连续供给所述惰性气体，其中所述惰性气体在步骤(i)和(ii)中用作载气和稀释气体并且在步骤(v’)和(vi’)中用作所述回蚀气体的至少一部分。
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