CN108987271A - 使用氢等离子体进行原子层蚀刻的方法 - Google Patents
使用氢等离子体进行原子层蚀刻的方法 Download PDFInfo
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- CN108987271A CN108987271A CN201810521891.3A CN201810521891A CN108987271A CN 108987271 A CN108987271 A CN 108987271A CN 201810521891 A CN201810521891 A CN 201810521891A CN 108987271 A CN108987271 A CN 108987271A
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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Abstract
一种用于通过干法蚀刻工艺蚀刻衬底上的目标层的方法包括至少一个蚀刻循环,其中蚀刻循环包括:在所述衬底上的所述目标层上使用反应性物质沉积碳卤化物膜;以及使用不含卤素的含氢蚀刻气体的等离子体蚀刻所述碳卤化物膜,所述等离子体单独地基本上不蚀刻所述目标层,从而在所述碳卤化物膜和所述目标层的边界区域生成作为蚀刻剂物质的卤化氢,由此蚀刻所述目标层在所述边界区域中的一部分。
Description
背景
发明领域
本发明整体涉及一种对例如由硅或金属氧化物构成的层进行循环干法蚀刻的方法。
相关技术描述
原子层蚀刻(ALE)是使用吸附在目标膜上的并且与激发的反应物质反应的蚀刻剂气体的循环原子层级蚀刻,如日本专利特许公开号2013-235912和2014-522104中所公开。与常规蚀刻技术相比,ALE可以在亚纳米级上执行精确的原子层级连续蚀刻以形成精细、窄的凸凹图案,并且可以适用于例如双重图案化工艺。作为蚀刻剂气体,Cl2、HCl、CHF3、CH2F2、CH3F、H2、BCL3、SiCl4、Br2、HBr、NF3、CF4、C2F6、C4F8、SF6、O2、SO2、COS等是已知的。然而,有证据显示,在蚀刻诸如氧化硅膜之类的氧化物矿物膜时,通过ALE蚀刻衬底上的膜的面内均匀性不令人满意。
当使用Cl2作为蚀刻剂气体通过ALE蚀刻Si或GaAs时,可以获得相对良好的蚀刻面内均匀性。但是,使用诸如C4F8之类的碳氟化合物作为蚀刻剂气体通过ALE蚀刻氧化硅膜时,并未获得良好的蚀刻面内均匀性。这是因为,尽管事实是在传统上蚀刻剂气体的吸附有时被称为“化学吸附”,但是蚀刻剂气体通过物理吸附而不是化学吸附吸附在衬底的表面上。也就是说,常规ALE如下蚀刻金属或氧化硅膜:通过物理吸附在膜表面上的蚀刻剂气体(其中被吸附的蚀刻剂气体与被激发的物质反应),另外还通过在吹扫之后留在反应空间中的蚀刻剂气体,从而导致气相蚀刻。结果,蚀刻的面内均匀性变差。如果蚀刻剂气体化学吸附在衬底的表面上,则吸附是“化学吸附”,即化学饱和吸附,它是一个自限性吸附反应过程,其中沉积的蚀刻剂气体分子的量由反应性表面位点的数量决定并且与饱和后的前体暴露无关,并且蚀刻剂气体的供应使得反应性表面位点因而在每个循环中得到饱和(即,每个循环中吸附在表面上的蚀刻剂气体原则上具有一个分子的厚度)。当发生蚀刻剂气体在衬底表面上的化学吸附时,可以实现蚀刻的高面内均匀性。常规ALE即使称为“化学吸附”,实际上也通过物理吸附在衬底表面上吸附蚀刻剂气体(例如,SiO2和SiN)。如果蚀刻剂气体的吸附是化学吸附,则蚀刻的面内均匀性在逻辑上应该是高的,并且每个循环的蚀刻速率在表面被蚀刻剂气体分子饱和后不应该受到蚀刻剂气体的流量或蚀刻剂气体流动脉冲的持续时间的影响。然而,传统的蚀刻剂气体都不符合上述要求。
对与相关技术相关的问题和解决方案的以上及任何其他论述已仅出于向本发明提供背景的目的包括于本公开中,并且不应被视为承认论述中的任一项或全部在创作本发明时是已知的。
发明内容
在一些实施方案中,由蚀刻剂的组分构成的膜(其可以被称为“蚀刻剂膜”)被沉积在目标层的表面上,然后将蚀刻剂膜以及目标层用等离子体处理来蚀刻。通过进行沉积步骤和蚀刻步骤并根据需要交替地重复它们,在每次进行沉积步骤和蚀刻步骤作为蚀刻循环时,可以将目标层蚀刻基本恒定的预定量。在上文中,蚀刻剂组分最初不作为蚀刻目标层的蚀刻剂气体,而是在目标层的表面上形成膜。在本公开中,“膜”是指基本上没有针孔的在与厚度方向垂直的方向上连续延伸的层,以覆盖整个目标或目标的相关表面,并且典型地,膜通过使用反应性物质进行反应,而不是简单地通过将气体分子化学或物理吸附在表面上而形成;因此随着沉积过程的继续,膜可以在厚度方向上生长超过原子层厚度。此外,“沉积膜”不仅仅在目标层表面上提供反应性位点,而且还物理沉积具有一定厚度的膜。
在一些实施方案中,当沉积在目标层表面上的蚀刻剂膜被反应性离子如氢等离子体蚀刻时,蚀刻剂膜的组分被解离并与反应性离子反应,从而生成反应性蚀刻剂物质,其可在蚀刻剂膜与目标层之间的边界处蚀刻目标层的一部分。在上文中,由于需要在边界附近生成反应性蚀刻剂物质,因此只有边界处的蚀刻剂膜的一定厚度才能有助于目标层的蚀刻反应。此外,由于蚀刻蚀刻剂膜的反应性离子不蚀刻目标层,因此当蚀刻剂膜被反应性离子去除时,目标层的蚀刻反应停止。因此,通过上述方法,恒定量的目标层总是可以通过一个蚀刻循环被蚀刻,因此,蚀刻过程的可控性和可操作性高。
例如,当目标层由SiO2构成时,通过等离子体增强CVD或热CVD将碳氟化合物膜(CF膜)作为蚀刻剂膜沉积在目标层的表面上,随后将蚀刻剂膜暴露于氢等离子体,以便去除蚀刻剂膜并同时蚀刻目标层的表面。在上文中,“同时”是指基本上或主要地同时发生或者基本上或主要地在时间上重叠发生。在上文中,随着蚀刻剂膜的厚度增加,目标层的蚀刻部分的深度增加;然而,当蚀刻剂膜的厚度达到一定值时,蚀刻部分的深度达到平稳期且不再增加。类似地,目标层的蚀刻部分的深度随着蚀刻剂膜暴露于等离子体的持续时间增加而增加;然而,当蚀刻剂膜暴露于等离子体的持续时间达到一定值时,蚀刻部分的深度达到平稳期且不再增加。也就是说,在一些实施方案中,上面讨论的蚀刻过程是具有两个参数的自限性反应过程,这两个参数具有饱和点。
在上文中,通过氢等离子体将CF膜作为诸如CH4、HF等气体去除,并且在SiO2层的表面附近的区域中,SiO2层的一部分也同时作为诸如SiF4、H2O等气体而去除。只有CF膜的靠近边界的一部分才有助于去除SiO2层的该部分,而CF膜的剩余部分不会帮助去除SiO2层,而只是通过氢等离子体去除。因此,SiO2层的蚀刻部分的深度相对于CF膜的厚度达到平稳期。另外,由于使用氢等离子体进行的SiO2层的蚀刻仅在存在CF膜时有效,因此在去除(用尽)CF膜时,SiO2层的蚀刻停止,即,SiO2层的蚀刻部分的深度也相对于氢等离子体暴露的持续时间达到平稳期。
在一些实施方案中,目标层可以由可以使用衍生自CF膜的卤化氢蚀刻的任何材料(例如SiO2、TiO2)构成。上述蚀刻对于构成目标层的材料具有高选择性,因此,例如,可以选择性蚀刻由硅或金属氧化物构成的膜,而基本上不蚀刻由硅或金属氮化物或碳化物构成的膜。在一些实施方案中,只要选择合适的蚀刻剂膜,目标层就可以由可以使用氟以外的卤素蚀刻的材料构成。典型地,蚀刻剂膜在反应性离子蚀刻(RIE)过程中暴露于氧等离子体。由于蚀刻过程涉及自限性反应过程(或饱和过程),所以可实现高可控性。
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,未必所有这些目的或优势都可以根据本发明的任何特定实施方案来实现。因此,举例来说,本领域的技术人员将认识到,本发明可以按实现或优化如本文中教示的一种优势或一组优势的方式实施或进行,而不必实现如本文中可能教示或提出的其他目的或优势。
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。附图出于说明性目的而被大大简化并且未必按比例绘制。
图1是可用在本发明实施方案中的等离子体辅助循环蚀刻设备的示意图。
图2显示了根据本发明实施方案的一个循环中的等离子体辅助循环蚀刻的示意性工艺顺序,其中该顺序中示出的步骤表示ON状态,而该顺序中未示出的步骤表示OFF状态,并且每个ON和OFF状态的长度不代表每个过程的持续时间。
图3示出了根据本发明实施方案的蚀刻过程的一个循环的示意图,其中(a)表示沉积步骤,(b)表示预蚀刻步骤,并且(c)表示蚀刻步骤。
图4是显示了根据本发明实施方案的原子层蚀刻(ALE)的流程图。
具体实施方式
在本公开中,“气体”可以包括气化的固体和/或液体并且可以由单一气体或气体混合物构成。在本公开中,通过喷头引入反应室中以进行沉积的工艺气体可以包括蚀刻剂气体和添加剂气体、主要由其组成或由其组成。添加剂气体通常包括用于稀释蚀刻剂气体并且与处于激发态时的蚀刻剂气体反应的稀释气体。蚀刻剂气体可以用载气如稀有气体引入。另外,不作为工艺气体的气体,即不穿过喷头而引入的气体,可以用于例如密封反应空间,所述气体包括密封气体,诸如稀有气体。在一些实施方案中,术语“蚀刻剂气体”通常是指参与蚀刻衬底上的目标层的蚀刻反应的至少一种气态的或蒸发的化合物,特别涉及在激发态下沉积在目标层上并在被等离子体激活时蚀刻目标层的至少一种化合物。术语“反应物气体”是指有助于蚀刻剂膜的沉积、蚀刻剂膜的激活或催化蚀刻剂膜的组分的蚀刻反应的至少一种气态的或蒸发的化合物。反应物气体可以用作吹扫气体。稀释气体和/或载气可以用作“反应物气体”。术语“载气”是指处于非激发态的惰性或非活性气体,其以混合状态将蚀刻剂气体带到反应空间并作为包括蚀刻剂气体的混合气体进入反应空间。
另外,在本公开中,由于可工作范围可以基于常规工作确定,因此变量的任何两个数字可以构成所述变量的可工作范围,并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(不管它们是否用“约”指示)都可以指精确值或近似值并且包含等效值,并且在一些实施方案中可以指平均值、中值、代表值、大部分值等。此外,在一些实施方案中,术语“由……构成”和“具有”独立地指“典型地或广泛地包括”、“包括”、“基本上由……组成”或“由……组成”。另外,冠词“一个(种)”是指某个种或包括多个种的某个属。在本公开中,在一些实施方案中,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。在所有所公开的实施方案中,出于预定目的,实施方案中所使用的任何要素都可以用与其等效的任何要素替代,包括本文中明确地、必要地或内在地公开的那些要素。此外,本发明可以同等地应用于设备和方法。
实施方案将参照优选实施方案进行阐述。然而,本发明不限于这些优选实施方案。
一些实施方案提供了一种通过包括至少一个蚀刻循环的干法蚀刻工艺来蚀刻衬底上的目标层的方法,其中蚀刻循环包括:(i)在衬底上的目标层上使用反应性物质沉积碳卤化物膜,其中碳卤化物膜和目标层彼此接触;以及(ii)(1)使用不含卤素的含氢蚀刻气体的等离子体蚀刻碳卤化物膜而不蚀刻目标层,该等离子体单独地基本上不蚀刻目标层,从而(2)在碳卤化物膜和目标层的边界区域生成作为蚀刻剂物质的卤化氢,由此蚀刻目标层在边界区域中的一部分。步骤(i)中的“反应性物质”基本上不蚀刻目标层,而是在目标层上形成蚀刻剂膜。在本公开中,“基本上零”等等(例如,“基本上不蚀刻”)可以指不重要的数量、小于可检测数量、不实质性影响目标或预期特性的数量,或技术人员认为几乎为零的数量,如在一些实施方案中相对于总值或参考值小于10%、小于5%、小于1%或其任何范围。
在一些实施方案中,目标层由硅或金属氧化物构成,其中金属可以是Ti、W、Ta等,例如SiO2、金属氧化物(例如TiO2)、或可用卤化氢等进行蚀刻的单独的金属。当蚀刻剂气体包含Cl或Br时,目标层可以由Al2O3、AlN、GaAs、GaN、GaP、InP等构成。在一些实施方案中,当蚀刻剂气体包含Cl时,目标层可以由聚氯乙烯构成。技术人员可根据需要基于常规实验来确定蚀刻剂气体和目标层的可能组合。在一些实施方案中,通过等离子体增强CVD、热CVD、循环CVD、等离子体增强ALD、热ALD、自由基增强ALD或任何其他薄膜沉积方法,在包括侧壁和底部表面的沟槽或通孔中和/或在平坦表面中形成目标层。通常,目标层的厚度在约50nm至约500nm的范围内(如根据膜的应用和目的等认为适当,可选择期望的膜厚度)。
在一些实施方案中,在步骤(i)中,碳卤化物膜通过气相反应沉积,其中反应性物质是由卤素和碳构成的一种或多种蚀刻剂气体的反应性物质。在一些实施方案中,卤素是F、Cl或Br。在一些实施方案中,可以使用包括常规蚀刻剂气体(例如,在“相关技术”章节中讨论的)的任何合适的蚀刻剂气体。由于步骤(i)中的蚀刻剂气体不用作直接蚀刻目标层的反应性蚀刻气体,而是充当用于沉积的气体,因此优选的是,蚀刻剂气体是具有双键或三键的CxFy,其中x和y是整数且x至少为2,例如C2F2、C2F4、C3F6、C4F8、C5F8、C5F10或前述物质的任何组合。这些气体往往容易形成处于激发态的含氟聚合物。在步骤(i)中,选择反应物气体以便沉积蚀刻剂膜,而不是蚀刻目标层,例如不使用含氧气体,因为氧等离子体从蚀刻剂气体生成用于蚀刻氧化硅膜等的活性蚀刻物质。在一些实施方案中,反应物气体是惰性气体,例如Ar和He。在一些实施方案中,通过选择合适的反应物气体和其他沉积条件,可以使用通常用于蚀刻氧化硅膜的蚀刻剂气体,例如CF4、C2F6、C3F8、C4F10等。
在一些实施方案中,在步骤(i)中,可以使用不含氟的蚀刻剂气体来沉积蚀刻剂膜。例如,可以使用烷基卤化物如C2H3Cl。此外,SF6、HCl、HBr等可以与诸如CH4的烃结合使用。
在一些实施方案中,可通过诸如原子层沉积(ALD)的表面反应来沉积蚀刻剂膜,其中蚀刻剂气体化学吸附到目标层的表面上,随后将该表面暴露于反应物气体的反应性物质。
在一些实施方案中,步骤(i)使用作为等离子体增强CVD的气相反应。在一些实施方案中,等离子体增强CVD包括:(a)向放置衬底的反应空间连续供给惰性气体;(b)向反应空间连续供给碳卤化物气体;以及(c)在不激发惰性气体和碳卤化物气体的情况下经过步骤(a)和(b)的预设持续时间之后,将RF功率施加到反应空间以将碳卤化物膜沉积在目标层上,其中在步骤(i)至(iii)中不向反应空间供给氧化气体。在上文中,术语“连续”取决于实施方案是指不中断空间(例如,在衬底上的不间断供应)、不中断流动(例如,不间断的流入)和/或以恒定的速率(该术语不需要同时满足所有前述条件)。在一些实施方案中,“连续的”流动具有恒定的流量(另选地,即使流动是“连续的”,其流量仍可以随时间的推移而改变)。在一些实施方案中,步骤(c)的持续时间短于步骤(a)和(b)的预设持续时间。由于将RF功率短时间施加到反应空间用于沉积,因此在施加RF功率之前用碳卤化物气体充满反应空间是重要的。
在一些实施方案中,步骤(i)持续进行,直到碳卤化物膜的厚度落入0.5nm至10nm,优选1nm至5nm的范围内,该范围接近平稳期厚度(或饱和厚度),超过该范围时,即使碳卤化物膜的厚度进一步增加,步骤(ii)中的目标层的蚀刻量也不会增加。
在一些实施方案中,步骤(i)的持续时间与目标层的蚀刻部分的厚度相关,直到即使步骤(i)的持续时间增加目标层的蚀刻部分的厚度也达到平稳期,并且步骤(i)继续进行直到目标层的蚀刻部分的厚度达到平稳期或平稳期附近的点。早前在本公开中讨论了上述机制,但是这些机制无意限制本发明。
在一些实施方案中,步骤(ii)继续进行,直到碳卤化物膜基本上被完全蚀刻,表明蚀刻了目标层的边界区域的基本上整个部分。在上文中,“基本上整个”等等可以指比该整体少了不重要的数量、可检测的数量、不实质性影响目标或预期特性的数量,或技术人员认为值无关紧要的数量,如在一些实施方案中相对于总值或参考值小于10%、小于5%、小于1%或其任何范围。优选地,步骤(ii)继续进行直到碳卤化物膜被完全蚀刻,表明目标层的边界区域的整个部分被完全去除。目标层的“边界区域”被定义为当碳卤化物膜被完全蚀刻时被蚀刻的区域。当碳卤化物膜的残留物残留在目标层的表面上时,残留物可能至少部分地干扰目标层的蚀刻,从而影响目标层的蚀刻深度的面内均匀性。
在一些实施方案中,在步骤(ii)中,目标层的蚀刻部分的厚度为0.1nm至2.0nm,优选0.5nm至1.0nm,其比原子层蚀刻(ALE)中限定的单层的小于0.1nm/循环的厚度更厚。
在一些实施方案中,在步骤(ii)中,不含卤素的含氢蚀刻气体是氢气或氨气、或者氢气或氨气与稀有气体的混合物。在一些实施方案中,含氢蚀刻气体不含氧。然而,可以选择任何合适的反应物气体以激活蚀刻剂膜以通过反应性离子蚀刻来蚀刻目标层。在一些实施方案中,稀有气体(如Ar和He气体)或氮气可以与含氢气体组合用作反应物气体。
在一些实施方案中,在步骤(ii)中,通过反应性离子蚀刻(RIE)来蚀刻碳卤化物膜。RIE可以是电感耦合等离子体蚀刻或电容耦合等离子体蚀刻。在一些实施方案中,电容耦合等离子体蚀刻包括:(a)向放置衬底的反应空间连续供给反应物气体;以及(b)在不激发反应物气体的情况下经过步骤(a)的预设持续时间之后,将RF功率施加到反应空间以蚀刻碳卤化物膜和目标层。
在一些实施方案中,将包括步骤(i)和(ii)的蚀刻循环重复至少两次,直到获得目标层的期望蚀刻深度。由于蚀刻循环是自限性蚀刻过程或饱和过程,所以目标层的蚀刻深度与所执行的循环次数成正比。
在一些实施方案中,步骤(i)和步骤(ii)在同一反应室中连续进行。在上文中,“连续”一词取决于实施方案是指以下项中的至少一项:不破坏真空、不暴露于空气、不打开腔室、作为原位过程、没有中断地作为顺序中的一个步骤、不改变工艺条件以及不在步骤之间在衬底表面上引起化学变化。在一些实施方案中,在上下文中诸如吹扫或其他可忽略步骤之类的辅助步骤不被视为一个步骤,因此,“连续”一词不排除辅助步骤的介入。
参考附图解释了一些实施方案,但这些实施方案无意限制本发明。
图3示出了根据本发明实施方案的蚀刻过程的一个循环的示意图,其中(a)表示沉积步骤,(b)表示预蚀刻步骤,并且(c)表示蚀刻步骤。在沉积步骤(步骤(a))之前,在反应空间中提供在其上形成目标层42的衬底41(例如,硅晶片或其他半导体晶片)。在沉积步骤中,在目标层42上以不小于饱和厚度T1的厚度沉积碳卤化物膜(蚀刻剂膜)43,其中碳卤化物膜43和目标层42彼此接触。饱和厚度T1被定义为这样一种厚度,蚀刻剂膜的一部分超过该厚度不会有助于蚀刻目标层,即,即使蚀刻剂膜的厚度进一步增加超过饱和厚度T1,目标层的蚀刻量也不增加。在预蚀刻步骤(步骤(b))中,蚀刻剂膜43暴露于诸如氢等离子体(氢自由基H*)之类的等离子体,从而蚀刻蚀刻剂膜,从其生成气态组分如烃气体和卤化氢等,并例如通过以下化学反应去除饱和厚度T1以上的蚀刻剂膜43的顶部部分(其中蚀刻剂膜由CxFy构成,其中x和y是整数):
CxFy+(4x+y)H*→xCH4+yHF (1)
由于碳氟化合物的组成根据沉积方法、蚀刻剂气体的类型等而变化,所以上述反应是一般反应并且被简化。此外,虽然可以生成除CH4以外的碳氢化合物,但此类碳氢化合物可能最终分解成CH4,因此反应可以由CH4表示。经过反应(1),通过氢自由基,可以从蚀刻剂膜中去除碳组分,同时生成HF组分,其继而蚀刻SiO2膜。
当蚀刻剂膜43的蚀刻进行并且蚀刻剂膜43被蚀刻到饱和厚度T1时,来自蚀刻剂膜43的诸如HF等气态组分同时从具有深度T2的目标层42的一部分通过使用HF气体在边界区域44通过例如以下化学反应生成诸如SiF4、2H2O等气态组分:
SiO2+4HF→SiF4+2H2O (2)
通过反应(2),SiO2膜被蚀刻,其中生成的H2O可以进一步辅助蚀刻反应。该蚀刻是化学蚀刻,因此,例如在SiO2与SiN之间的蚀刻选择性可以非常高(针对SiO2的蚀刻速率高,但针对SiN的蚀刻速率基本为零),并且还可以执行保形蚀刻(均匀蚀刻)。这些特征不能通过传统的蚀刻方法来实现。
边界区域44由具有饱和厚度T1的蚀刻剂膜43的边界区域和具有深度T2的目标层42的边界区域构成。边界区域的总厚度(T1+T2)可以取决于等离子体中的离子能量,例如取决于RF功率和反应空间的压力。边界区域44可以由诸如SiCOF的混合组分构成的中间体组成。如反应(1)和(2)所示,预蚀刻步骤(步骤(b))由两个步骤构成,其中第一步是蚀刻蚀刻剂膜(例如碳卤化物膜)并通过氢自由基生成蚀刻剂物质(例如卤化氢),而第二步是通过蚀刻剂物质蚀刻目标层。第二步可以在没有等离子体(没有施加RF功率)的情况下进行,而第一步使用等离子体。然而,第一步和第二步彼此重叠,即,在第一步结束之前开始通过蚀刻剂物质蚀刻目标层的第二步。
在蚀刻步骤(步骤(c))中,边界区域或中间层44作为气态组分被去除,其中目标层42被蚀刻深度T2以获得蚀刻目标层45。应该注意的是,虽然步骤(b)和(c)分开显示以便于理解步骤的原理,但这些步骤相反地同时发生。由于单独的等离子体基本上不会蚀刻目标层,所以当边界区域44被去除时,目标层45的蚀刻停止。
在一些实施方案中,该过程可以如图4所示执行,该图显示了原子层蚀刻(ALE)的流程图。在步骤a中,通过等离子体增强或热CVD或可优选地执行保形沉积(例如,六氟环氧丙烷(HFPO)热沉积)的任何合适方法来沉积CF膜。在步骤b(吹扫反应空间)之后,在步骤c中,将CF膜暴露于氢等离子体,由此在目标层(例如SiO2)的表面处生成HF。在该过程中,氢自由基的存在可能是足够的,或者除此之外,在一些实施方案中,可能还需要离子轰击。在步骤c之后,在步骤d中吹扫反应空间。步骤a至d构成ALE的一个循环,其可以重复多次直到蚀刻目标层的期望厚度。由于蚀刻剂膜(CF膜)暴露于氢等离子体并被蚀刻,而目标层不暴露于氢等离子体,因此对目标层造成较少的等离子体损伤或基本上没有等离子体损伤。
在一些实施方案中,可以如图2所示设置工艺顺序。图2显示了根据本发明实施方案的一个循环中的等离子体辅助循环蚀刻的示意性工艺顺序,其中该顺序中示出的步骤表示ON状态,而该顺序中未示出的步骤表示OFF状态,并且每个ON和OFF状态的长度不代表每个过程的持续时间。在该实施方案中,一个蚀刻循环包括沉积步骤(在该实施方案中为等离子体增强CVD)和蚀刻步骤。沉积步骤包括“步骤1”,而蚀刻步骤包括“吹扫1”、“步骤2”、“步骤3”和“吹扫2”。
在作为等离子体增强CVD步骤的沉积步骤的“步骤1”中,诸如Ar和/或He的稀释气体被连续地供给到放置衬底的反应空间中,而碳卤化物气体连续地供给到反应空间,同时连续地将RF功率施加到反应空间而不供给氢气。在沉积步骤的“步骤1”中,将具有期望厚度(例如,0.5nm至10nm,典型地约2nm)的含卤素膜(例如,碳卤化物膜)作为蚀刻剂膜沉积在目标层上。步骤1是蚀刻剂膜(沿着与厚度方向垂直的方向延伸而没有针孔,并且完全覆盖目标层的相关区域)的沉积步骤,该步骤不仅仅是在目标层上提供反应性位点的步骤。沉积步骤可以是任何合适的沉积步骤,包括热CVD、PVD、PEALD等的沉积步骤,并且技术人员可以相应地容易地修改“步骤1”。
在“步骤1”之后,开始蚀刻步骤的“吹扫1”,其中氢气(蚀刻气体)被连续地供给到反应空间而不供给稀释气体和碳卤化物气体且不施加RF功率。蚀刻气体可以是含有氢的气体,例如氨,或含氢气体与稀有气体(例如Ar、He)的混合物。“吹扫1”用于去除未反应的产物、不需要的副产物和任何剩余的沉积气体,并用于稳定反应空间且准备进行蚀刻。在经过“吹扫1”的预设持续时间之后,在“步骤2”中,将RF功率施加到反应空间以蚀刻含卤素膜(蚀刻剂膜,例如碳卤化物膜)和目标层,同时供给氢气(蚀刻气体)而不供给含卤素气体以生成氢自由基,氢自由基由于与诸如碳卤化物的蚀刻剂膜反应,继而生成蚀刻剂物质,诸如卤化氢。诸如卤化氢的蚀刻剂物质在目标层与含卤素膜之间的边界区域化学蚀刻与蚀刻剂物质接触的目标层表面。在“步骤2”中,目标层的化学蚀刻开始并随着诸如卤化氢的蚀刻剂物质的生成而继续,并且在停止氢气流动和RF功率的施加的“步骤3”中,因为一些蚀刻剂物质剩余,剩余的蚀刻剂物质继续蚀刻目标层表面,直到剩余的蚀刻剂物质被消耗或“吹扫2”开始。任何合适的用于生成氢自由基的手段均可用于“步骤2”中。“步骤2”的持续时间可以根据含卤素膜的厚度等来确定。在“步骤2”中,将整个含卤素膜蚀刻或去除。“步骤3”的持续时间可以根据“步骤2”结束时剩余的卤化氢的量以及目标层表面需要蚀刻多少等来确定。在“吹扫3”中,反应空间通过供给稀释气体而被吹扫以去除未反应的产物、不需要的副产物和任何剩余的蚀刻剂物质。该蚀刻循环可以重复进行,直到蚀刻目标层的期望深度。
在“步骤2”中,使用RF功率来生成包含氢自由基的氢等离子体,并因此或另选地,例如通过使用远程等离子体单元,也可以产生包含氢自由基的氢等离子体。在一些实施方案中,RF功率以脉冲施加。
在一些实施方案中,蚀刻循环可以在下表1中所示的条件下进行。
表1(数值是近似值)
在图2所示的顺序中,含卤素气体可以使用可以连续供给到反应空间的载气来供应,特别是当含卤素气体是液体材料的蒸发气体时,例如C5F8、C5F10等。这可以使用流通切换系统(FPS)实现(例如,在2015年8月18日提交的美国专利申请号14/829,565中公开的系统,该专利的公开内容全文以引用方式并入),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供给到反应室时,关闭绕道管线,而当打算将载气和前体气体供给到反应室时,关闭主管线,并且载气流过绕道管线并且与前体气体一起从瓶中流出。通过这种方式,载气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。
在一些实施方案中,目标层由单独的Si、单独的金属、前述物质的氧化物或前述物质的碳酸盐构成,因此可以选择可形成蚀刻剂膜(含卤素膜)的合适的蚀刻剂气体(含卤素气体),蚀刻剂膜在被氢自由基蚀刻时继而生成蚀刻剂物质。例如,当目标层由SiO2构成时,蚀刻剂气体适当地含有F作为卤素,而当目标层由Si构成时,蚀刻剂气体适当地含有Cl作为卤素。本领域的技术人员根据本公开并通过常规实验可以容易地选择用于目标层的合适的蚀刻剂气体。下表2显示了实例。由于蚀刻剂物质的蚀刻过程具有高选择性,所以例如可以选择性地仅蚀刻氧化硅而保持氮化硅。蚀刻剂膜可以由可通过氢自由基分解产生蚀刻剂物质如卤化氢的碳卤化物构成。氢自由基可以由含有氢的蚀刻剂气体或含氢气体和稀有气体的混合物产生。
表2(合适的组合)
目标层 | 蚀刻剂膜 |
Si、Al(可溶于HCl的金属) | CCl膜(通过PVC等) |
Ti、W(可溶于HCl的金属) | CF膜 |
氧化硅 | CF膜 |
氮化硅 | 不可蚀刻 |
金属氧化物(例如TiO) | CF膜 |
工艺循环可以使用任何合适的设备进行,包括例如图1中所示的设备。图1是可用在本发明的一些实施方案中的等离子体辅助循环蚀刻设备的示意图,该设备宜与被编程以进行下文所描述的工序的控制装置结合。在这个图中,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。温度调节器被设置于下部平台2(下部电极)中,并且其上放置的衬底1的温度恒定保持在指定温度。上部电极4也充当喷淋板,并且稀有气体、反应物气体和蚀刻剂气体分别通过气体管线21、22和23并通过喷淋板4引入反应室3中。另外,在反应室3中,设置了具有排气管线7的环形管道13,反应室3的内部11中的气体通过所述环形管道被排出。另外,通过气体管线23将稀释气体引入反应室3中。另外,设置在反应室3下方的转移室5具备密封气体管线24以将密封气体经由转移室5的内部16(转移区)引入反应室3的内部11中,在该转移室中设置有用于隔离反应区与转移区的隔离板14(本图中省略闸阀,晶片通过所述闸阀转移至转移室5中或从转移室5转移)。转移室还具备排气管线6。在一些实施方案中,在同一反应空间中进行多元素膜的沉积和表面处理,使得所有步骤可以连续进行而不将衬底暴露于空气或其他含氧气氛。在一些实施方案中,远程等离子体单元可以用于激发气体。
在一些实施方案中,可以使用双室反应器(用于加工彼此靠近设置的晶片的两个部分或隔室),其中反应剂气体和稀有气体可以通过共享管线供应而前体气体通过未共享管线供应。在一些实施方案中,沉积步骤可以使用不同于蚀刻步骤的设备来执行。
技术人员将了解,所述设备包括一个或多个被编程或以其他方式配置成使得沉积和本文其他地方所述的反应器清洁过程能够进行的控制器(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、机器人装置以及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阐述本发明。然而,这些实施例无意限制本发明。在未指定条件和/或结构的实施例中,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这类条件和/或结构。同样,在一些实施方案中,可以将具体实施例中所应用的数值修改至少±50%的范围,并且数值是近似值。
实施例
实施例1(预示性实施例)
分别在300mm衬底上通过PEALD或PECVD作为目标层以约20nm的厚度形成氧化硅膜、氮化硅膜和碳化硅膜。使用图1所示的等离子辅助蚀刻设备,在下表3所示的条件下,进行蚀刻剂膜(CF膜)的蚀刻和各目标层的蚀刻。每个蚀刻循环中使用的顺序如图2所示。
表3(数值是近似值)
对于每个衬底,将包括沉积步骤和蚀刻步骤的蚀刻循环重复3次和6次。蚀刻循环之后,通过椭圆光度法测量每个目标层的厚度。结果,SiO2膜的每个循环的蚀刻速率(EPC)约为0.7nm/循环,而SiN膜和SiC膜的每个循环的蚀刻速率几乎为零,即基本上不降低膜厚度。
本领域的技术人员应理解,在不脱离本发明的精神的情况下可以进行大量和各种修改。因此,应清楚地理解,本发明的形式仅是说明性的,并且不打算限制本发明的范围。
Claims (19)
1.一种通过包括至少一个蚀刻循环的干法蚀刻工艺来蚀刻衬底上的目标层的方法,其中蚀刻循环包括:
(i)在所述衬底上的所述目标层上使用反应性物质沉积碳卤化物膜,其中所述碳卤化物膜和所述目标层彼此接触;以及
(ii)(1)使用不含卤素的含氢蚀刻气体的等离子体蚀刻所述碳卤化物膜而不蚀刻所述目标层,所述等离子体单独地基本上不蚀刻所述目标层,从而(2)在所述碳卤化物膜和所述目标层的边界区域生成作为蚀刻剂物质的卤化氢,由此蚀刻所述目标层在所述边界区域中的一部分。
2.根据权利要求1所述的方法,其中步骤(ii)继续进行,直到所述碳卤化物膜基本上被完全蚀刻,表明蚀刻了所述目标层的所述边界区域的基本上整个部分。
3.根据权利要求1所述的方法,其中步骤(i)的持续时间与所述目标层的蚀刻部分的厚度相关,直到即使步骤(i)的所述持续时间增加所述目标层的所述蚀刻部分的所述厚度也达到平稳,并且步骤(i)继续进行直到所述目标层的所述蚀刻部分的所述厚度达到所述平稳期或所述平稳期附近的点。
4.根据权利要求1所述的方法,其中所述蚀刻循环重复至少两次。
5.根据权利要求1所述的方法,其中步骤(i)继续进行,直到所述碳卤化物膜的厚度落在0.5nm至10nm的范围内。
6.根据权利要求1所述的方法,其中在步骤(ii)中,所述目标层的所述蚀刻部分的厚度为0.1nm至2.0nm。
7.根据权利要求1所述的方法,其中在步骤(i)中,所述碳卤化物膜通过气相反应沉积,其中所述反应性物质是由卤素和碳构成的一种或多种蚀刻剂气体的反应性物质。
8.根据权利要求7所述的方法,其中所述卤素是F或Cl。
9.根据权利要求8所述的方法,其中所述卤素是F,并且所述蚀刻剂物质是HF。
10.根据权利要求8所述的方法,其中所述蚀刻剂气体是具有双键或三键的CxFy,其中x和y是整数且x至少为2。
11.根据权利要求7所述的方法,其中所述气相反应是等离子体增强CVD。
12.根据权利要求11所述的方法,其中所述等离子体增强CVD包括:
(a)向放置所述衬底的反应空间连续供给惰性气体;
(b)向所述反应空间连续供给碳卤化物气体;以及
(c)在不激发所述惰性气体和所述碳卤化物气体的情况下经过步骤(a)和(b)的预设持续时间之后,将RF功率施加到所述反应空间以将所述碳卤化物膜沉积在所述目标层上,其中在步骤(a)至(c)中不向所述反应空间供给氧化气体。
13.根据权利要求12所述的方法,其中步骤(c)的持续时间短于步骤(a)和(b)的预设持续时间。
14.根据权利要求1所述的方法,其中在步骤(ii)中,所述不含卤素的含氢蚀刻气体为氢气或氨气、或者氢气或氨气与稀有气体的混合物,且不含氧气。
15.根据权利要求1所述的方法,其中在步骤(ii)中,通过反应性离子蚀刻(RIE)来蚀刻所述碳卤化物膜。
16.根据权利要求15所述的方法,其中所述RIE是电容耦合等离子体蚀刻。
17.根据权利要求16所述的方法,其中所述电容耦合等离子体蚀刻包括:
(a)向放置所述衬底的反应空间连续供给反应物气体;以及
(b)在不激发所述反应物气体的情况下经过步骤(a)的预设持续时间之后,将RF功率施加到所述反应空间以蚀刻所述碳卤化物膜和所述目标层。
18.根据权利要求1所述的方法,其中所述目标层由SiO2、金属氧化物或可通过卤化氢蚀刻的金属构成。
19.根据权利要求1所述的方法,其中步骤(i)和步骤(ii)在同一反应室中连续进行。
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