CN108122739A - 拓扑限制的等离子体增强循环沉积的方法 - Google Patents
拓扑限制的等离子体增强循环沉积的方法 Download PDFInfo
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- CN108122739A CN108122739A CN201711181019.0A CN201711181019A CN108122739A CN 108122739 A CN108122739 A CN 108122739A CN 201711181019 A CN201711181019 A CN 201711181019A CN 108122739 A CN108122739 A CN 108122739A
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/14—Cyanic or isocyanic acid; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/04—Coating on selected surface areas, e.g. using masks
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
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Abstract
本申请公开了一种拓扑限制的等离子体增强循环沉积的方法。在一个实施例中,一种用于将由间隔地布置于模板上的垂直间隔物构成的图案转移到所述模板的方法包括:通过等离子体增强循环沉积将作为间隔伞层的层基本上仅沉积于由氧化硅或金属氧化物制成的每一垂直间隔物的顶部表面上,其中基本上无层沉积于所述垂直间隔物的侧壁上和所述模板的暴露表面上,随后通过各向异性蚀刻使用具有所述间隔伞层的所述垂直间隔物,将由所述垂直间隔物构成的所述图案转移到所述模板。
Description
相关申请的交叉引用
本申请依据35 USC 119(e)要求2016年11月28日申请的美国临时申请第62/426,804号的权益,所述临时申请的公开内容以全文引用的方式并入本文中。
技术领域
本发明大体上涉及一种等离子体增强循环沉积的方法,特别地一种拓扑限制的等离子体增强循环沉积的方法,其称作拓扑实现选择性沉积(topology-enabling selectivedeposition)或TESD,其中膜选择性沉积于沟槽之间的顶部表面上。这种技术不被视为ALD,但其最初使用等离子体增强原子层沉积(PEALD)设备导出,并且由此这种技术最初称作地形实现选择性ALD或GESA。由于发明人已使用“GESA”来表示这种技术,因此在本公开中,术语“GESA”用以指拓扑实现选择性沉积。同样,在本公开中,与本发明相关,术语“ALD”或“PEALD”是指在适用于ALD或PEALD的设备中的循环沉积,而非涉及原子层沉积或等离子体增强ALD。
背景技术
作为在衬底上沉积电介质膜的方法,通常化学气相沉积(CVD)和原子层沉积(ALD)是已知的。所属领域的技术人员经常使用等离子体增强CVD(PECVD)和等离子体增强ALD(PEALD)来形成电介质膜。PEALD是使用前体的化学吸附的电介质膜沉积技术,并且相比于PECVD,可以改良沉积于衬底凹槽图案上的膜的步阶覆盖。然而,当通过PEALD将不为SiO膜的电介质膜沉积于凹槽图案上时,其中在具有等离子体的气氛中进行硝化或碳取代反应,相对于沉积于顶部表面上的膜的厚度,沉积于侧壁上的膜的厚度有时较小。这一问题可能由相比于顶部或底部表面,干扰侧壁上的反应速度的离子碰撞引起。特别地,相比于氧化,硝化具有低的侧壁反应速率,引起薄膜沉积于侧壁上、沉积于侧壁上的膜的劣化等问题。通常,凹槽图案中通过PEALD的膜的保形性(沉积于侧壁上的SiN或SiCN膜的厚度与沉积于顶部表面上的膜的厚度的比率(百分比))可以在60%到90%范围内。尽管沉积具有高保形性的膜具有优势,但本发明人已发现沉积具有基本上零保形性的膜具有显著优势,即,在例如使用间隔物界定双图案化(SDDP)的图案转移和目标蚀刻的工艺中,基本上无膜沉积于凹槽图案的侧壁上,其中通过使用呈基本上仅沉积于垂直间隔物的顶部表面上的硬掩模形式的膜,可以有效地避免工艺期间任何可能的优先蚀刻(其经常发生在某些结晶取向中)和分辨率损失。本发明人已进行研究以在PEALD中沉积具有基本上零保形性的膜。
对与相关技术相关的问题和解决方案的任何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
一些实施例提供一种将由间隔地布置于模板上的垂直间隔物构成的图案转移到模板的方法,包含:通过等离子体增强原子层沉积(PEALD),将作为间隔伞层的层基本上仅沉积于由氧化硅或金属氧化物制成的每一垂直间隔物的顶部表面上,其中基本上无层沉积于垂直间隔物的侧壁上和模板的暴露表面上;随后通过各向异性蚀刻使用具有间隔伞层的垂直间隔物,将由垂直间隔物构成的图案转移到模板。由于层基本上仅沉积于每一垂直间隔物的顶部表面上而基本上无层沉积于凹槽图案的侧壁和底部上,因此层是拓扑限制层并且可以有效地充当间隔伞层。由于基本上无层沉积于侧壁和底部上,因此在将图案转移到模板之前不需要额外工艺从侧壁和底部去除这类层。上文PEALD不同于常规PEALD,因为常规PEALD作为将高度共形膜沉积于沟槽中的方法而众所周知,然而与常规PEALD相反,上文PEALD是用于沉积非共形膜-即其保形性基本上为零-的方法。由于上文PEALD沉积拓扑限制膜,因此拓扑限制PEALD被称作拓扑实现选择性沉积或GESA。
其它实施例提供一种通过等离子体增强原子层沉积(PEALD)循环,将膜基本上仅沉积于具有由底部和侧壁构成的凹槽图案的衬底的顶部表面上的方法,其中每一循环包含:(i)在不向放置衬底的反应空间施加RF功率的情况下,使用运载气体通过含有呈液体状态的前体的瓶,将前体供应到反应空间,所述前体含有除氢以外的多种元素,其中瓶中的蒸气压是约30mmHg或更高;和(ii)在不供应前体的情况下向反应空间施加RF功率,由此将拓扑限制层基本上仅沉积于衬底的顶部表面上,其中基本上无层沉积于凹槽图案的侧壁和底部上。
如上文所论述,尽管GESA代表拓扑实现选择性ALD,但GESA本质上不是ALD,因为相比于使得高度共形膜能够在厚度方面几乎均一地沉积于凹槽图案的所有表面上的常规ALD,GESA使得膜能够选择性或基本上仅沉积于凹槽图案的顶部表面上,即,膜的基本上零保形性(侧壁处的膜厚度与顶部表面处的膜厚度的比率)。此外,不同于ALD,GESA具有CVD组分。即,每一循环沉积的子层的厚度大于原子层的厚度,即,比通过自限制吸附工艺而化学吸附于表面上的前体的厚度更厚。因此,在本公开中,尽管使用术语“GESA”,但GESA不是指ALD工艺并且还可以称作“拓扑实现选择性沉积”(TESD)。GESA不限于上文所描述的实施例并且更一般化地可以通过例如拓扑实现选择性沉积的方法来进行,其中在[冠词或多个]半导体制造层中,膜选择性沉积于具有由底部和侧壁构成的凹槽图案的衬底的顶部表面上,所述方法依序包含:(i)将前体供应到衬底放置在电极之间的反应空间,所述前体除金属或类金属原子以外含有包括氮的多种元素;(ii)净化反应空间,仅达到与化学吸附于衬底的顶部表面上的前体的量相比更大量的前体保留在衬底的顶部表面附近的程度;和(iii)在电极之间施加RF功率,同时供应基本上不含H和O的等离子体产生气体,以产生衬底暴露于其的富离子各向异性等离子体,由此将拓扑限制层基本上仅或选择性并占优势地沉积于衬底的顶部表面上,其中基本上无层或基本上比拓扑限制层更薄沉积于凹槽图案的侧壁和底部上。GESA的独特特征,例如高度非共形生长,适用于许多半导体制造工艺,例如公开于本公开中的那些工艺,并且所属领域的技术人员将了解这类适用的应用并且将能够在这类应用中基于本公开并且通过常规实验进行GESA。
此外,在一些实施例中,所述方法在步骤(iii)后进一步包含(v)在反应空间中将步骤(iii)中获得的拓扑限制层暴露于氧气等离子体,以将为基于氮化物的层、基于含氮碳化物的层或碳氮化物层的拓扑限制层转化成基于氧化物的层。与上文转化过程组合,GESA的应用广泛地延伸到各种半导体制造工艺。
出于概述本发明的方面和优于相关技术而实现的优势的目的,本发明的某些目标和优势描述于本公开中。当然,应理解,未必所有这类目标或优势可以根据本发明的任何特定实施例来实现。因此,举例来说,所属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,而不必须获得如本文中可以教示或表明的其它目标或优势。
本发明的其它方面、特征和优势将从之后的实施方式变得显而易见。
附图说明
现将参考优选实施例的图式来描述本发明的这些和其它特征,所述优选实施例在于说明并且不限制本发明。所述图式出于说明性目的被大大简化并且未必按比例。
图1A是可用于本发明的一个实施例的用于沉积电介质膜的PEALD(等离子体增强原子层沉积)设备的示意性图示。
图1B说明使用流通系统(flow-pass system,FPS)的可用于本发明的一个实施例的前体供应系统的示意性图示。
图2显示使用一种前体的根据本发明的一个实施例的一个循环的低于大气压PEALD的示意性过程顺序,其中灰色单元表示开启状态而白色单元表示断开状态,并且每个单元的宽度不表示每个过程的持续时间。
图3是显示根据本发明的一个实施例的GESA膜的X射线衍射概况的图。
图4是显示根据本发明的一个实施例的沉积于沟槽上的GESA膜的截面视图的STEM照片。
图5是显示根据本发明的一个实施例的沉积于沟槽上的GESA膜的截面视图的STEM照片。
图6是显示根据本发明的一个实施例的沉积于沟槽上的GESA膜的截面视图的STEM照片。
图7是显示根据一比较实例的沉积于沟槽上的PEALD(不完全GESA)膜的截面视图的STEM照片。
图8是根据本发明的一个实施例的使用间隔物界定双图案化(SDDP)的图案转移和目标蚀刻(步骤(a)到(j))的示意性图示。
图9是根据本发明的一个实施例的(a)中的CVD、(b)中的PEALD、(c)中的改进PEALD(不完全GESA)和(d)中的GESA的沉积概况的示意性图示。
图10是根据本发明的一个实施例的通过氧气等离子体的氧化工艺的示意性图示,其中(a)中的硅/金属氮化物转化成硅/金属氧化物。
图11是显示根据本发明的一个实施例的沉积于具有沟槽的衬底上的GESA膜的截面视图的STEM照片。
图12是显示根据本发明的一个实施例的在暴露于氧气等离子体时显示于图11中的GESA膜的截面视图的STEM照片。
图13显示根据本发明的实施例的在暴露于氧气等离子体之前(GESA POR)、在使用400W RF功率暴露于氧气等离子体时(TS-SiO400W)、并且在使用100W RF功率暴露于氧气等离子体时(TS-SiO100W)的GESA膜的XPC光谱。
图14是根据本发明的一个实施例的在形成虚设栅极凹槽中施用GESA膜的示意性图示,其中(a)显示无GESA膜的问题并且(b)显示通过GESA膜实现的有利作用。
具体实施方式
在本公开中,取决于背景,“气体”可以包括气化固体和/或液体并且可以由单一气体或气体混合物构成。同样,取决于背景,冠词“一(a/an)”是指一种物种或包括多种物种的属。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。添加剂气体可以包括用于氮化和/或碳化前体的反应气体和当向添加剂气体施加RF功率时用于激发前体的惰性气体(例如,稀有气体)。惰性气体可以作为运载气体和/或稀释气体馈送到反应室。在本公开中,不使用用于氧化前体的反应气体。此外,在一些实施例中,不使用反应气体,并且仅使用稀有气体(作为运载气体和/或稀释气体)。前体和添加剂气体可以作为混合气体或单独地引入到反应空间。前体可以用运载气体如稀有气体引入。不为工艺气体的气体,即,在不穿过喷头的情况下引入的气体,可以用于例如密封反应空间,其包括密封气体如稀有气体。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,然而术语“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功率时反应物可以向膜基质提供元素(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。
在一些实施例中,“膜”是指在垂直于厚度方向的方向上连续延伸的层,基本上无针孔覆盖整个目标或相关表面;或简单地覆盖目标或相关表面的层。在一些实施例中,“层”是指形成于表面上的具有某一厚度的结构或膜或非膜结构的同义词。膜或层可以由具有某些特征的离散单一膜或层或多个膜或层构成,并且邻近膜或层之间的边界可以透明或可以不透明,并且可以基于物理、化学和/或任何其它特征,形成过程或顺序和/或邻近膜或层的功能或目的而确立。此外,在本公开中,由于可工作范围可以基于常规工作确定,因此变数的任何两个数字可以构成变数的可工作范围,并且所指示的任何范围可以包括或排除端点。另外,所指示的变数的任何值(与它们是否用“约”指示无关)可以指精确值或近似值并且包括等同物,并且在一些实施例中可以指平均值、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”独立地是指“通常或广泛地包含”、“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。
在未指定条件和/或结构的本公开中,鉴于本公开,所属领域的技术人员可以按照常规实验容易地提供这类条件和/或结构。
在所有的所公开实施例中,出于既定目的,实施例中所使用的任何元素可以用与其同等的任何元素替换,包括本文中明确、必须或本质上所公开的那些元素。此外,本发明可以同等地应用于设备和方法。
实施例将参照优选实施例而阐述。然而,本发明不限于优选实施例。
在一些实施例中,用于将由间隔地布置于模板(通常由通过旋涂或CVD工艺制备的非晶碳(a-C)构成)上的垂直间隔物构成的图案转移到模板的方法包含:通过等离子体增强原子层沉积(PEALD)将作为间隔伞层的层基本上仅沉积于由氧化硅或金属氧化物(例如,TiO2)制成的每一垂直间隔物的顶部表面上,其中基本上无层沉积于垂直间隔物的侧壁上和模板的暴露表面上;随后通过各向异性蚀刻(例如,反应性离子蚀刻,RIE)使用具有间隔伞层的垂直间隔物将由垂直间隔物构成的图案转移到模板。
在本公开中,在一些实施例中,“基本上零”等等可以指不重要的数量、小于可检测数量、不显著地影响目标或既定特性的数量,或所属领域的技术人员认为几乎为零的数量,如相对于总值或参考值小于10%,小于5%,小于1%或其任何范围。举例来说,当具有10nm厚度的膜沉积于顶部表面上,并且基本上无膜沉积于侧壁上时,沉积于侧壁上的膜的厚度可以小于1nm,小于0.5nm,小于0.1nm或其间的任何范围。在本公开中,在一些实施例中,“基本上更薄”、“基本上较短”等等可以指实质差异或所属领域的技术人员所认可的差异,如至少30%、40%、50%、60%、70%、80%、90%。或其任何范围的那些差异。举例来说,当具有10nm厚度的膜沉积于顶部表面上,并且基本上比所述膜更薄的层沉积于侧壁上时,沉积于侧壁上的膜的厚度可以是至多7nm,至多6nm,至多5nm,至多4nm,至多3nm,至多2nm,至多1nm或其间的任何范围。同样,举例来说,当持续1秒完成净化以从目标区域中充分去除过量气体、未反应气体和副产物并且进行基本上短净化时,这类短净化的持续时间可以是至多0.7秒,至多0.6秒,至多0.5秒,至多0.4秒,至多0.3秒,至多0.2秒,至多0.1秒或其间的任何范围。此外,在本公开中,在一些实施例中,“基本上相同”、“基本上均一”等等可以指不重要的差异或所属领域的技术人员所认可的差异,如小于10%、小于5%、小于1%或其任何范围的那些差异。
由于呈硬掩模形式的间隔伞针对底层模板具有高蚀刻选择性,因此垂直间隔物可以较短并且因此可以蚀刻期间维持以将图案转移到模板。在一些实施例中,垂直间隔物的高度在3nm到60nm、通常约5nm到约40nm的范围内。在一些实施例中,间隔伞层的厚度在约1nm到约15nm、通常约3nm到约8nm范围内。在一些实施例中,间隔伞层由非晶氮化硅碳构成。在一些实施例中,模板由非晶碳构成。在一些实施例中,垂直间隔物通过间隔物界定双图案化(SDDP)产生。
在一些实施例中,对于拓扑限制PEALD或拓扑实现选择性PEALD(GESA),邻近垂直间隔物之间的每一间距必须小于预定距离。在本公开中,邻近垂直间隔物之间的凹槽和任何其它凹槽图案被称作“沟槽”。也就是说,沟槽是包括由垂直间隔物形成的图案的任何凹槽图案并且其在一些实施例中具有约20nm到约100nm(通常约30nm到约50nm)的宽度(其中当沟槽具有基本上与宽度相同的长度时,其被称作孔/通孔,并且其直径是约20nm到约100nm)、约30nm到约100nm(通常约40nm到约60nm)的深度和约2到约10(通常约2到约5)的纵横比。沟槽的适当尺寸可以取决于工艺条件、膜组成、既定应用等而改变。
在上文中,如果沟槽的宽度太宽,那么GESA变得不完全,并且不完全GESA膜可以自然地开始沉积于沟槽的底部表面上,并且因此在理论上(在不限制本发明的情况下),沟槽的宽度可以经过选择,使得CVD的非共形沉积概况可以如下文所描述明显。在非限制性理论中,在CVD的非共形沉积概况会明显、施用各向异性等离子体、和蚀刻/溅镀概况会明显的条件下,GESA可以是完全的。在GESA的某些条件下,可以增强并且促进上文现象以使膜基本上不沉积于侧壁和底部表面上。
图9是根据本发明的一个实施例的(a)中的CVD、(b)中的PEALD、(c)中的改进PEALD(不完全GESA)和(d)中的GESA的沉积概况的示意性图示。当沟槽较窄时,蘑菇形生长是CVD的典型沉积概况,所述CVD包括如图9(a)中所说明的循环CVD,其中当膜102沉积于具有沟槽的衬底101上时,沉积于顶部表面上的其顶部部分较厚,沉积于侧壁上的其侧部分比顶部部分更薄并且朝向沟槽底部变得更薄,并且沉积于底部表面上的其底部部分较薄或几乎检测不到或不可检测。在CVD中,以气相激发的前体的反应性物种不充分地到达窄沟槽的底部。在PEALD中,共形生长是如图9(b)中所说明的典型沉积概况,其中当膜103沉积于具有沟槽的衬底101上时,沉积于顶部表面上的其顶部部分、沉积于侧壁上的其侧部分和沉积于底部表面上的其底部部分是拓扑共形的。在PEALD中,不同于CVD,膜通过表面反应形成,其中前体分子吸收于沟槽的所有表面上并且是饱和的,其中饱和后所吸附的前体分子的量与前体暴露无关(即,自限制吸附反应工艺)。净化后,所吸收的前体分子暴露于反应气体,随后暴露于等离子体,引起表面反应,以形成膜。当使用各向异性等离子体如Ar等离子体时,等离子体不充分地到达沟槽的侧壁。众所周知,等离子体组合物是复杂的,由带电(离子)或中性(原子和自由基)中的许多不同物种构成。通常可接受的是在等离子体中,离子物种负责高度各向异性生长并且负责所谓的“离子轰击”。举例来说,Ar等离子体大部分由具有极少自由基的离子构成,使得Ar等离子体工艺通常具有极不良的保形性并且呈现图9(c)中所说明的沉积概况(改进PEALD或不完全GESA),其中沉积于顶部表面上的其顶部部分较厚,沉积于侧壁上的其侧部分较薄或几乎检测不到或不可检测,并且沉积于底部表面上的其底部部分较厚。在侧壁上,发生不充足的离子轰击,而轰击充分地到达顶部和底部表面。
相比之下,GESA的沉积概况说明于图9(d)中,其中沉积于顶部表面上的其顶部部分较厚,沉积于侧壁上的其侧部分和沉积于底部表面上的其底部部分较薄或几乎检测不到或不可检测。在非限制性理论中,发生GESA,其中CVD的非共形沉积概况会明显,各向异性等离子体被施用,并且蚀刻/溅镀概况会明显。也就是说,例如,当通过升高储存呈液体形式的前体的瓶的温度而增加前体的蒸气压,达到供应比饱和量多得多的高量前体(剂量可以比饱和量高至少一个数量级)的程度时,使得净化不足以去除所有前驱气体。以气相形式存在的残余前驱气体可能引起类CVD沉积,其中蘑菇概况更明显。此外,残余前驱气体可以降低离子(例如,等离子体中所含有的Ar离子)的平均自由路径,由此使离子更难以到达沟槽的底部表面(在沟槽底部离子轰击较小)。平均自由路径可以定义如下(简化为平均距离/碰撞):
其中d是分子的直径,并且nv是每单位体积分子的数目。也就是说,当每体积分子的数目增加时离子的平均自由路径变短。举例来说,前体分子的直径显著大于Ar离子的直径,并且像云悬停的残余前体分子将显著缩短离子的平均自由路径。同样,通过增加工艺压力,nv增加,由此缩短离子的平均自由路径。因此,在GESA中,于沟槽的底部表面上的膜形成被有效抑制,由此基本上无膜沉积于沟槽的底部表面上,而膜形成在沟槽的顶部表面上进行(顶部表面上方的残余前体分子可以有助于膜形成,并且因此当在GESA中延长RF功率施加的持续时间时,不同于常规PEALD,生长速率/循环会增加)。为了将残余前体分子保持在衬底上方,有效参数中的一种是增加前体的分压,即,增加前体的蒸气压而非延长前体脉冲的持续时间。此外,如上文所描述,使用各向异性等离子体阻止膜沉积于沟槽的侧壁上。
此外,在非限制性理论中,蚀刻/溅镀作用可以对GESA沉积概况有贡献。考虑到Ar离子束可以用于溅镀,等离子体中所含有的Ar离子可以将所沉积膜中的一些溅镀掉。在典型GESA中,所沉积膜的生长速率极低(例如GESA工艺一般具有极低生长速率,例如0.06-0.1埃/循环),并且溅镀可以对它有贡献。此外,对于低密度膜(例如,GESA膜由50%碳和20%氢构成,或具有Si和N污染物的低密度(20%H2)a-C膜),这类溅镀作用可能更明显。在一些实施例中,可以按以下方式操纵通过Ar等离子体轰击的溅镀:(Dt-St)>(Db-Sb)≥(Ds-Ss)其中Dt、Db和Ds分别表示沟槽的顶部表面处、底部表面处和侧壁处的沉积速率,并且St、Sb和Ss分别表示沟槽的顶部表面处、底部表面处和侧壁处的溅镀速率。在一些实施例中,Sb>Db,并且Ss>Ds。此外,前体和Ar等离子体的反应副产物可以对GESA沉积概况有贡献。归因于前体的组成,例如包括Si、N、C和H,一些H离子/自由基在等离子体暴露期间产生。当GESA膜主要由a-C构成时,这类碳膜对通过H物种(挥发性产物)的攻击高度敏感。因此,为进一步使顶部选择性概况最佳化,在一些实施例中,可以按以下方式操纵蚀刻作用:(Dt-Et)>(Db-Eb)≥(Ds-Es)其中Dt、Db和Ds分别表示沟槽的顶部表面处、底部表面处和侧壁处的沉积速率,并且Et、Eb和Es分别表示沟槽的顶部表面处、底部表面处和侧壁处的通过激发副产物的蚀刻速率。在一些实施例中,Eb>Db,并且Es>Ds。前体剂量、净化程度、等离子体的持续时间、工艺压力和惰性气体流量在使GESA沉积概况最佳化的关键参数中。
在一些实施例中,沉积于沟槽的顶部表面上的GESA膜的厚度依据沟槽的宽度选择,以便将膜基本上仅沉积于顶部表面上(基本上无膜沉积于底部表面和侧壁上)。举例来说,当沟槽的宽度(W)是约6nm时,顶部表面上膜的厚度(T)可以小于约9nm,通常约7nm或更小,然而当沟槽的宽度(W)是约3nm时,顶部表面上膜的厚度(T)可以小于约18nm,通常约14nm或更小,其中T(nm)×W(nm)可以小于约54,通常42或更小。
在本发明的另一个方面中,一些实施例提供一种通过等离子体增强原子层沉积(PEALD)循环,将膜基本上仅沉积于具有由底部和侧壁构成的凹槽图案的衬底的顶部表面上的方法,其中每一循环包含:(i)在不向放置衬底的反应空间施加RF功率的情况下,使用运载气体通过含有呈液体状态的前体的瓶,将前体供应到反应空间,所述前体含有除氢以外的多种元素,其中瓶中的蒸气压是约30mmHg或更高;和(ii)在不供应前体的情况下向反应空间施加RF功率,由此将拓扑限制层基本上仅沉积于衬底的顶部表面上,其中基本上无层沉积于凹槽图案的侧壁和底部上。
在一些实施例中,无反应物贯穿PEALD循环供应到反应空间,并且仅运载气体(优选Ar)用于等离子体反应。由于前体含有除氢以外的多种元素,因此不需要反应物来沉积GESA膜。在一些实施例中,由于不使用反应物,因此前体是在其分子中含有除氢以外的多种元素的任何合适前体。在一些实施例中,前体含有硅/金属、氮、碳和氢。在一些实施例中,替代硅或除硅以外,前体含有金属,如Ti、Zr、Co、W、Ta、Hf和/或Nb。在一些实施例中,前体是烷氨基硅烷。在一些实施例中,烷氨基硅烷选自由以下组成的群组:双二乙氨基硅烷(BDEAS)、双二甲基氨基硅烷(BDMAS)、己乙基氨基硅烷(HEAD)、四乙基氨基硅烷(TEAS)、叔丁基氨基硅烷(TBAS)、双叔丁基氨基硅烷(BTBAS)、双二甲基氨基二甲基氨基硅烷(BDMADMS)、七甲基硅氮烷(HMDS)、三甲基硅烷基二乙胺(TMSDEA)、三甲基硅烷基二甲胺(trimethylsyledimethlamine,TMSDMA)、三甲基toribinyl环三硅氮烷(trimethyltoribinylcycletrisilazane,TMTVCTS)、三三甲基羟基胺(TTMSHA)、双二甲基氨基甲基硅烷(bisdimethylsaminomethylsilane,BDMAMS)和二甲基硅烷基二甲胺(DMSDMA)。前体可以由单一前体或两种或更多种前体的混合物构成。
在一些实施例中,烷氨基硅烷前体从储存器或瓶供应到反应室用于非晶氮化硅碳层的GESA。烷氨基硅烷前体在室温下通常(而不是必须)是液体,并且当在反应室的上游需要前体气化时,前体在配备有加热器的储存器或瓶中气化。供应到反应室的前体的数量可基于从储存器排放的前体的蒸气压测定,蒸气压通过储存器的温度测定。在一些实施例中,与针对氧化硅层的PEALD的储存器温度(例如,针对BDEAS约20℃到约60℃)相比,针对非晶氮化硅碳层的GESA的储存器温度更高(例如,针对BDEAS约70℃到约100℃,例如通常约80℃)。举例来说,BDEAS的饱和蒸气压在70℃下是30mmHg,并且因此对于GESA可以需要30mmHg或更高(例如,35mmHg或更高)的蒸气压以便向反应空间供应某一剂量的前体。举例来说,80℃下前体的剂量可以比例如60℃下前体的剂量高至少一个数位。出人意料地,对于GESA,前体的蒸气压是一种重要的工艺参数,因为在常规ALD中前体的化学吸附受自限制饱和吸附控制。对于GESA,前体的剂量需要足够高以阻断膜在沟槽的底部表面和侧壁处的沉积,但顶部表面上的膜厚度不显著受剂量影响。剂量可以影响电磁场在沟槽的每个顶部表面处的产生,以抑制膜在沟槽的底部和侧壁处沉积。剂量还可以由瓶温度、进料时间、运载气体流量和稀释气体流量限定。
此外,在一些实施例中,RF功率以每单位面积(cm2)衬底约50W到约1000W(通常约75.W/cm2到约500W/cm2)施加到反应空间。在一些实施例中,针对非晶氮化硅碳层的GESA的RF功率高于或等于针对氧化硅层的PEALD的RF功率,例如,针对300mm衬底在约100W到约500W范围内(W值可以转化成每单位面积衬底的瓦数并且施加到具有不同大小的衬底)。还出人意料地,当RF功率施加的持续时间变得更长时,生长速率/循环(GPC)可以显著增加(超过50%),指示与经由简单饱和吸附相比,更多的前体分子吸附于衬底表面上,其中施加RF功率更长时间可以对使用衬底上方的残余前体分子的类CVD沉积有贡献,但所述理论不限制本发明。鉴于上文,GESA具有典型ALD的基础特征,但根本上或在化学上不同于典型ALD。
在一些实施例中,运载气体通过PEALD循环连续供应到反应室。在一些实施例中,稀释气体贯穿PEALD循环连续供应到反应空间。作为运载气体和稀释气体,稀有气体如Ar、He、Ne、Kr和Xe可以单独使用或以两种或更多种的任何组合形式使用。
在本公开中,在一些实施例中,“连续”是指不中断真空,不中断为时间线,无任何材料插入步骤,不改变处理条件,其后立即,作为下一步骤,或在不为两个结构的两个结构之间不插入离散物理或化学结构。
在一些实施例中,循环进一步包含在每一循环中在步骤(i)后净化反应室,并且在步骤(ii)后净化反应空间。
在一些实施例中,GESA层沉积于由氧化硅或金属氧化物制成的底层上。在一些实施例中,作为底层,SiO层通过例如PEALD(如公开于由同一申请人于2015年12月21日提交的美国申请第14/977,291号中的PEALD,所述申请的公开内容以全文引用的方式并入本文中)沉积于具有沟槽的衬底上。在一些实施例中,SiO层使用烷氨基硅烷作为前体来沉积,所述烷氨基硅烷是与非晶氮化硅碳层的GESA中所用的气体相同的气体。在一些实施例中,底层和GESA层连续沉积于同一反应室中。
在一些实施例中,尽管SiO层具有80%到100%的保形性,但可以获得沉积于SiO层上并且具有基本上零保形性的GESA层,即使SiO层和GESA层连续沉积于同一反应室中也如此。理论上(不限制本发明的情况下),当适当地选择沟槽的宽度时,通过调节如本公开中所描述的工艺条件,可以抑制沟槽的底部和侧壁处的离子轰击,并且可以部分地发生类CVD沉积,其中衬底上方的残余前体分子(通过例如不充分净化和/或升高的瓶温度,缩短离子的平均自由路径)可以阻断等离子体中所包括的入射离子进入沟槽中,并且各向异性等离子体还可以降低沟槽的侧壁处的离子轰击,由此抑制膜于沟槽的侧壁和底部表面上的沉积。在GESA的某些条件下,可以增强并且促进上文现象以使膜基本上不沉积于侧壁和底部表面上。
尽管通常使用SiO层,但底层可以是其它电介质膜(优选由针对GESA可以促进累积电荷的材料构成)。这类电介质膜包括但不限于由SiC、SiCO、任何掺杂硅玻璃或介电常数是约1.9到5.0、通常约2.1到3.0、优选小于2.5的有机聚合物或硅类聚合物构成的低k膜。在一些实施例中,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或任何其它薄膜沉积方法,电介质膜形成于包括侧壁和底部表面的沟槽或通孔和/或平坦表面中。通常,电介质膜的厚度在约50nm到约500nm范围内(如根据膜的应用和目的等认为适当,可选择所期望的膜厚度)。
实施例将参照图式而阐述。然而,本发明不限于图式。
图2显示根据本发明的一个实施例的一个循环的GESA的示意性连续过程顺序,其中灰色单元表示开启状态而白色单元表示断开状态,并且每个单元的宽度不表示每个过程的持续时间。在图2中所说明的顺序中,在不施加RF功率的情况下,使用连续供应的运载气体将前体以脉冲(“进料”)形式供应到反应空间。同样,将稀释气体连续供应到反应空间。在“进料”后,净化反应空间(“净化1”),其中在不施加RF功率的情况下,无前体馈送到反应空间,而运载气体和稀释气体连续馈送到反应空间,由此从衬底表面去除非化学吸附前体和过量气体。其后,在不馈送前体的情况下,通过施加RF功率(“RF”),以脉冲(“RF”)形式在贯穿沉积循环连续流动的运载气体和稀释气体中原位产生用于沉积的等离子体,由此形成单层。在“RF”后,净化反应空间(“净化2”),其中在不馈送前体并且在不施加RF功率到反应空间的情况下,运载气体和稀释气体连续馈送到反应空间,由此从衬底表面去除副产物和过量气体。由于进入反应空间的运载气体作为恒定流(前体间歇地或以脉冲方式注射于其中)连续流动,并且由于稀释气体连续流动,因此可以有效进行净化以从层表面快速去除过量气体和副产物,由此有效地继续多个PEALD循环。
在GESA中,尽管前体的单层因ALD的性质形成于包括沟槽的顶部表面、侧壁和底部表面的所有表面上,但由于等离子体不到达形成于沟槽的侧壁和底部表面上的部分单层,因此基本上无膜形成于沟槽的侧壁和底部表面上,并且部分单层通过净化去除。
在图2中,借助运载气体提供前体。由于ALD是自限制吸附反应工艺,因此所沉积前体分子的数目通过反应性表面部位的数目测定,并且饱和后与前体暴露无关,并且由此每一循环对前体的供应使得反应性表面部位是饱和的。如上文所提及,每一沉积循环的每一脉冲或阶段优选是自限制的。在每一阶段供应过量的前体以使敏感的结构表面饱和。表面饱和确保前体占据所有可用的反应性部位(例如经历物理大小或“位阻”限制)。在一些实施例中,可以降低前体的脉冲时间,使得不实现完全饱和并且小于一单层吸附于衬底表面上。
运载气体的连续流动可以使用流通系统(FPS)实现,其中运载气体管线具备具有前体储存器(瓶)的绕道管线,主管线和绕道管线经切换,其中当打算仅将运载气体馈送到反应室时,关闭绕道管线,而当打算将运载气体和前驱气体馈送到反应室时,关闭主管线,并且运载气体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携带呈脉冲形式的前驱气体。图1B说明根据本发明的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)中所显示,当将前体馈送到反应室(未显示)时,首先,运载气体如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)20。运载气体从瓶20中流出,同时携载量对应于瓶20内部的蒸气压的前驱气体,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。当仅将运载气体(稀有气体)馈送到反应室时,如图1B中的(b)中所显示,运载气体流过具有阀的气体管线,同时绕过瓶20。在上文中,阀b、c、d、e和f是关闭的。
所属领域的技术人员将了解,设备包括一个或多个被编程或以其它方式被配置成使得进行沉积和本文中其它地方所描述的反应器清洁工艺的控制器(未显示)。如所属领域的技术人员将了解,控制器连通有各种电源、加热系统、泵、机器人技术和反应器的气体流量控制器或阀。
举例来说,过程循环可以使用任何合适的设备包括图1A中所说明的设备来进行。图1A是PEALD设备的示意图,所述设备宜与被编程以进行下文所描述的顺序的控制装置结合,可用于本发明的一些实施例。在这个图中,通过提供一对并联的并且在反应室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)25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。温度调节器提供于下部阶段2(下部电极)中,并且放置于其上的衬底1的温度在指定温度下保持恒定。上部电极4也充当喷淋板,并且反应气体和/或稀释气体(如果存在的话)和前驱气体分别通过气体管线21和气体管线22引入反应室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的环形管道13,通过其反应室3的内部11中的气体被排出。另外,在反应室3下方设置的转移腔室5具备密封气体管线24以将密封气体经由转移腔室5的内部16(转移区)引入反应室3的内部11中,在转移腔室中提供用于隔离反应区和转移区的隔离板14(从这个图中省略闸阀,通过其晶片转移于传递腔室5中或从传递腔室转移)。转移腔室还具备排气管线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,使得所有步骤可以连续进行而不将衬底暴露于空气或其它含氧气氛。
在一些实施例中,在图1A中所描绘的设备中,图1B中所说明的切换非活性气体的流量与前驱气体的流量的系统(在前面描述)可以用于引入呈脉冲形式的前驱气体而不基本上使反应室的压力波动。
所属领域的技术人员将了解,设备包括一个或多个被编程或以其它方式被配置成使得进行沉积和本文中其它地方所描述的反应器清洁工艺的控制器(未显示)。如所属领域的技术人员将了解,控制器连通有各种电源、加热系统、泵、机器人技术和反应器的气体流量控制器或阀。
在一些实施例中,可以使用双室反应器(用于加工彼此密切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以通过共享管线供应而前驱气体通过未共享管线供应。
在一些实施例中,GESA循环可以在下表1中所显示的条件下进行。
表1(数值是近似的)
针对300mm晶片的上文所指示的RF功率可以转化成W/cm2(每单位面积晶片的瓦数),其可以适用于具有不同直径如200mm或450mm的晶片。
在一些实施例中,GESA膜的厚度在约3nm到约30nm、通常约5nm到约15nm的范围内(还取决于沟槽的宽度,如根据膜的应用和目的等认为适当,可选择所期望的膜厚度)。因此,在一些实施例中,仅重复循环直到拓扑限制层的厚度达到高于所期望的厚度。
对于GESA,通常不使用反应气体,并且因此不同于常规ALD,在化学吸附前体后,不化学吸附反应物,其中在一些实施例中仅使用前体和惰性气体等离子体。因此,严格地说,在上文实施例中,GESA不是ALD,但GESA使用PEALD设备进行。
GESA层可以用于各种应用,包括间隔物界定双图案化(SDDP)。图8是根据本发明的一个实施例的使用SDDP的图案转移和目标蚀刻的示意性图示,其中GESA膜用作硬掩模以将图案从第一模板转移到第二模板。抗反射层(ARL)94用作用于在SDDP工艺中增加图案密度(例如,间距减小)的第一模板。蚀刻硬掩模82用作用于蚀刻目标层81的第二模板。在图8中的步骤(a)中,在抗反射层94(由例如非晶碳构成)上形成光致抗蚀剂图案93(由例如酚醛清漆构成),使得抗反射层94可以在步骤(b)中的光致抗蚀剂图案中蚀刻,所述步骤(b)是将图案转移到第一模板94的步骤。在步骤(c)中,金属氧化物间隔物95(由例如氧化硅构成)根据所公开实施例或与其的等同物中的任一个沉积,随后在为间隔物RIE(反应性离子蚀刻)步骤的步骤(d)中蚀刻。通过剥离抗反射层94的材料(核心部分96中的光致抗蚀剂材料),在步骤(e)中形成垂直间隔物84。由于金属氧化物间隔物(95)具有高蚀刻选择性,因此用于在其上形成间隔物的抗反射层94(第一模板)可以较薄,并且金属氧化物间隔物可以在蚀刻期间维持以在步骤(e)中形成垂直间隔物84(金属氧化物间隔物)。在一些实施例中,抗反射层的厚度是约5到50nm(通常10到30nm),并且金属氧化物层的厚度是约5到50nm(通常10到20nm)。在一些实施例中,GESA膜的厚度是约2到15nm(通常3到8nm)。在步骤(f)中,GESA膜72作为耐蚀刻间隔伞选择性沉积于垂直间隔物84的顶部上。拓扑限制PEALD实现膜的顶部选择性沉积。
在步骤(g)中,图案通过蚀刻从具有GESA膜72的垂直间隔物84转移到第二模板82以形成第二垂直间隔物74,并且在步骤(h)中,第一垂直间隔物84被剥离。在步骤(i)中,形成于硅衬底70上的目标层81使用第二垂直间隔物74经历干式蚀刻。在步骤(j)中,第二垂直间隔物74被剥离。在上文中,通过使用根据所公开实施例或与其的等同物中的任一个的GESA膜作为蚀刻抗蚀剂间隔伞72,可以有效并精确地将图案从第一模板94转移到第二模板82。此外,GESA膜可以有助于使间隔物保持完整并且在图案转移到第二模板期间提高分辨率。在一些实施例中,抗反射层、蚀刻硬掩模、金属氧化物层(间隔物)和目标层可以通过本文中所公开的方法或其等同物中的任一种或通过脉冲PECVD或PEALD来沉积。
GESA膜不仅对HF、HCl和TMAH湿式蚀刻具有抗性,而且还对例如BCl3、BCl3/Ar干式蚀刻具有抗性,并且因此在步骤(g)中,当将图案转移到第二模板82时,GESA膜帮助垂直间隔物84维持图案。另一方面,GESA膜对氧化、湿式蚀刻化学交替氧化和HF的组合(常见于半导体加工中)或基于氧或CF4的干式蚀刻敏感,并且因此在步骤(h)中,GESA膜可以与金属氧化物间隔物84一起被有效地剥离。
GESA不限于上文所描述的实施例并且可以更一般化地通过例如拓扑实现选择性沉积的方法来进行,其中在半导体制造中,膜选择性沉积于具有由底部和侧壁构成的凹槽图案的衬底的顶部表面上,所述方法依序包含:(i)将前体供应到衬底放置在电极之间的反应空间,所述前体除金属或类金属原子以外含有包括氮的多种元素;(ii)净化反应空间,仅达到与化学吸附于衬底的顶部表面上的前体的量相比更大量的前体保留在衬底的顶部表面附近的程度;和(iii)在电极之间施加RF功率,同时供应基本上不含H和O的等离子体产生气体,以产生衬底暴露于其的富离子各向异性等离子体,由此将拓扑限制层基本上仅或选择性并占优势地沉积于衬底的顶部表面上,其中基本上无层或基本上比拓扑限制层更薄的层沉积于凹槽图案的侧壁和底部上。GESA的独特特征,例如高度非共形生长,适用于许多半导体制造工艺,例如公开于本公开中的那些工艺,并且所属领域的技术人员将了解这类适用的应用并且将能够在这类应用中基于本公开并且通过常规实验进行GESA。本发明的额外、替代或修改的非限制性实施例将在下文详细地阐述,其中上文所公开的任何实施例中所描述的任何元素/条件可以按任何组合用于下文所描述的实施例,达到与用于实施例中的其它元素相容并且一致的完整程度。在所有的所公开实施例中,用于实施例中的任何元素可以用与其同等的任何其它元素替换,包括在本文中明确、必须或本质上所公开的那些元素,只要这类变化不相互矛盾即可。
在一些实施例中,不仅可以使用含有硅的前体,而且可以使用含有金属的前体。这类金属可以是至少一种选自由例如以下组成的群组的元素:Ti、Zr、Hf、Ti、Ta、Nb、Si、Ge、Al、Co、W、Ru、Cu、Ni、V、Zn和Pt,并且含有金属的这类前体包括但不限于SiH4、Si2H6、GeH4、WF6、TiCl4、HFCl4、(CH3)3Al、(CH3CH2)2Zn、Cp2Ni、(EtCp)2Ru、Cp2Me2Zr、(MeCp)(Me)3Pt、Al(NMe2)3、Al2(NMe2)6、Hf(NMe2)4、Hf(NEtMe)4、Hf(NEt2)4、La[N(SiMe3)2]3、Ta(NMe2)5、Ta(NEt2)5、Ta(NtBu)(NEt2)3、Ti(NMe2)4、Ti(NEtMe)4、W(NtBu)2(NMe2)2、Zn[N(SiMe3)2]2、Zr(NMe2)4、Zr(NEtMe)4、Zr(NEt2)4、V(NEt2)4、Co(iPr-amd)、Co(tBuEt-amd)2、Cu2(iPr2-amd)2、Ni(tBu2-amd)2、Cu2(sBu2-amd)2、Ti(iPr2-amd)3、V(Et2-amd)3、V(iPr2-amd)3、Hf(Me2-pmd)4和Hf(Me2-bmd)4。如在本公开中所论述,以下两个特征对通过GESA的拓扑限制沉积或顶部选择性沉积的机制有贡献:
a)产生高度非共形生长的所显现CVD组分(例如,不完全或基本上短的净化)。
b)基本上不含自由基的高度各向异性等离子体(例如,无含O2或H的气流作为等离子体产生气体通过腔室),其导致基本上较薄的膜沉积于侧壁上(如果O或H(如果存在的话)(优选无)含于正沉积的膜中,那么O或H的唯一来源应包括于前体中)。
如下文所说明,GESA原理不仅可以应用到含硅前体而且可以应用到含金属前体,如Ti(NCH3)4。
·Ti(NCH3)4+Ar或He等离子体→TiCN(拓扑限制)
此外,如下文所说明,可以应用公开于本公开中的沉积后氧化工艺。
·TiCN(拓扑限制)+O2等离子体(沉积后)→TiO(拓扑限制)
在一些实施例中,拓扑限制层由SiCN、SiN、TiCN、TiN、TaCN或TaN构成。
在一些实施例中,除等离子体产生气体以外无反应物贯穿沉积步骤供应到反应空间。
在一些实施例中,在步骤(i)中,在不在电极之间施加RF功率的情况下将前体供应到反应空间,并且所述方法进一步包含(iv)在步骤(ii)之后立即净化反应室,其中仅重复步骤(i)到(iv)直到拓扑限制层的厚度达到1nm到100nm。
在一些实施例中,等离子体产生气体基本上不含H和O(如NH3、CO2等),但由Ar、He和/或N2构成,因为这类气体可以产生富离子的自由基不足的各向异性等离子体。出于同一原因,远程等离子体不合适,因为远程等离子体主要含有自由基。富离子的自由基不足的等离子体可以定义为比来源于等离子体产生气体的自由基含有更多离子的等离子体,即,离子与自由基的比率大于一,这可以使用光学发射光谱法(optical emissionspectrometry,OES)测定。举例来说,在OES光谱中,391nm处的一个峰表示N2 +离子,并且601nm处的另一峰表示N2*中性物,其中比率可以定义为OES离子(391nm)/中性物(601nm)的比率。比率可以依据腔室压力和N2/He气体混合物改变,其中例如当压力低于10m托时并且当气体混合物富氦气(氦气比氮气更多)时,等离子体变得具有更多的离子。
如GESA的有效施用,在一些实施例中,凹槽图案是由间隔地布置于模板上的光致抗蚀剂线或垂直间隔物构成的图案,并且在步骤(iii)中,拓扑限制层作为伞层基本上仅沉积于每一光致抗蚀剂线或每一垂直间隔物的顶部表面上,其中层基本上不沉积于光致抗蚀剂线或垂直间隔物的侧壁上,也不沉积于模板的暴露表面上,随后通过各向异性蚀刻使用具有伞层的光致抗蚀剂线或垂直间隔物将由光致抗蚀剂线或垂直间隔物构成的图案转移到模板。也就是说,GESA膜不仅可以用作如前面所描述的间隔伞层,而且还用作抗蚀剂伞层。举例来说,拓扑限制层直接沉积于通过EUV(极紫外线)光刻形成的光致抗蚀剂线上。为对应于半导体装置的小型化,减少用于光刻的光源的波长,例如从ArF(氟化氩激光)变到EUV。然而,EUV的光致抗蚀剂似乎较弱。GESA膜可以增强EUV光致抗蚀剂。此外,通过将GESA膜沉积于EUV光致抗蚀剂上,可以增加光致抗蚀剂的高度,使得增加图案转移分辨率。在一些实施例中,抗蚀剂伞层的厚度在2nm到20nm范围内。
在一些实施例中,针对GESA膜直接沉积于EUV光致抗蚀剂上,用于沉积GESA膜的Ar等离子体(或He等离子体)可能不是所期望的,因为重Ar原子可能例如对比ArF光致抗蚀剂更脆的EUV光致抗蚀剂造成损害。在所述状况下,N2等离子体可用于替代Ar等离子体,由此沉积氮化硅而非碳氮化硅,例如如下文所说明:
·烷氨基硅烷+Ar等离子体→SiCN(拓扑限制)
·烷氨基硅烷+N2等离子体→SiN(拓扑限制)
通过使用N2等离子体替代Ar等离子体来沉积GESA膜,可以基本上抑制或降低对光致抗蚀剂的损害。除了Ar运载和稀释气体被N2运载和稀释气体替换(但其流动速率可以相同)以外,使用N2等离子体的方法条件可以与使用Ar等离子体的方法条件一致。
如GESA的另一有效施用,在一些实施例中,凹槽图案是由FinFET装置的fin结构构成的图案,并且在步骤(iii)中,拓扑限制层作为保护层基本上仅或选择性并占优势地沉积于由氧化硅或金属氧化物制成的每个fin结构的顶部表面上,其中基本上无层或基本上比拓扑限制层更薄的层沉积于fin结构的侧壁上和衬底的暴露表面上。
图14是根据本发明的一个实施例的在形成虚设栅极凹槽中施用GESA膜的示意性图示,其中(a)显示无GESA膜的问题并且(b)显示通过GESA膜实现的有利作用。在(a)中,为了在衬底201的顶部上形成薄硅Fin反转沟道,其允许栅极制成两个接触点,即,Fin 203的左侧和右侧(未显示),虚设栅极207最初覆盖Fin 203,所述Fin覆盖有厚度是2nm的SiO内衬205,例如如图14(a)中所说明。然后,去除虚设栅极207以通过蚀刻形成凹槽,由此形成Fin反转沟道。然而,如(a)中所说明,通过蚀刻,SiO内衬覆盖的Fin 203的顶部受损,即,沟道的特性降解。然而,如图14(b)中所说明,在蚀刻工艺期间通过在SiO内衬覆盖的Fin 203的顶部上选择性形成GESA膜209,以形成虚设栅极凹槽,SiO内衬覆盖的Fin 203的顶部可以有效地受保护,避免沟道劣化。
如上文所描述,所属领域的技术人员将了解GESA的特征,并且将能够基于本公开通过常规实验,通过利用GESA的主要功能来选择性保护不仅与图案化相关联而且与其它半导体制造工艺相关联的特定特征的顶部,而将GESA施用到各种应用。
此外,在一些实施例中,所述方法在步骤(iii)后(即,在沉积拓扑限制层后)进一步包含(v)在反应空间中将步骤(iii)中获得的拓扑限制层暴露于氧气等离子体,以将为基于氮化物的层的拓扑限制层转化成基于氧化物的层。与上文转化过程组合,GESA的应用广泛地延伸到各种半导体制造工艺。举例来说,当GESA膜用作非牺牲膜时,呈SiCN膜形式的GESA膜泄漏严重,对装置性能产生不利的作用。通过将其转化成氧化硅膜,膜质量可以得到显著改良。在半导体制造工艺中的另一实例中,通过将GESA膜转化成氧化物膜,可以调节膜的干式蚀刻速率选择性,其中在氧化物膜下集成可以变得更容易。在再一实例中,当制造需要通过HF浸渍的湿式蚀刻来去除层时,通过将构成层的GESA膜转化成氧化物层,可以有效地进行湿式蚀刻,因为呈SiCN膜形式的GESA膜通常不被HF蚀刻溶液蚀刻。
图10是根据本发明的一个实施例的通过氧气等离子体的氧化工艺的示意性图示,其中(a)中的硅/金属氮化物转化成硅/金属氧化物。在这个实施例中,如(a)中所说明,GESA膜105选择性沉积于具有沟槽的衬底101的顶部表面上,并且通过将GESA膜105暴露于氧气等离子体,在不显著蚀刻GESA膜的情况下,GESA膜可以转化成基于氧化物的膜106,如(b)中所说明。
在一些实施例中,形成于基于氧化物的底层上的拓扑限制层的厚度通过步骤(v)中的氧气等离子体处理而减小。
在一些实施例中,拓扑限制层沉积于基于氧化物的底层上,其中在步骤(v)中拓扑限制层完全转化成基于氧化物的层,使得拓扑限制层与底层之间基本上不存在可检测接缝。在实现上述的一种方式中,在一些实施例中,步骤(v)在重复步骤(i)到(iii)的每一预设次数后进行。在上文(循环暴露于氧气等离子体)中,在一些实施例中,在步骤(v)后拓扑限制层的总厚度即大于20nm(优选地,20nm到100nm)。或者,在一些实施例中,步骤(v)在完成步骤(i)到(iii)后作为沉积后处理而进行。在上文(单次暴露于氧气等离子体)中,在一些实施例中,拓扑限制层的总厚度在步骤(v)时在2nm到20nm(优选5nm到15nm)范围内。当拓扑限制层的厚度超过20nm时,每一次暴露于等离子体,通过等离子体的氧化可能不彻底地出现在比20nm更深的区域中。
在一些实施例中,基于氮化物的GESA膜转化成基于氧化物的膜可以使用氧气等离子体在下表1A中所显示的条件下进行。
表1A(数值是近似的)
以下表格显示GESA工艺和等离子体氧化工艺的组合的实例:
表1B(当使用烷氨基硅烷时)
表1C(当使用金属烷基酰胺时)
表1D(当使用金属卤化物时)
表1E(当使用金属醇盐时)
在上文中在表1B到1E中,运载气体和稀释气体用符号*指示,*意味着这些气体是否用于沉积工艺,但这些气体不是必不可少的。如果金属前体最初是气态或高度挥发性的液体,那么不需要运载气体,并且同样,如果使用运载气体,那么稀释气体可以是不必要的。
进一步参考下文的工作实例来阐述本发明。然而,所述实例并不打算限制本发明。在不指定条件和/或结构的实例中,鉴于本公开,所属领域的技术人员可以按照常规实验容易地提供这类条件和/或结构。同样,在一些实施例中,可以将具体实例中所应用的数值修改至少±50%的范围,并且数值是近似的。
实例
实例1
为确定膜的特性,通过GESA使用图2中所说明的顺序,在Si衬底(具有300mm的直径和0.7mm的厚度)的平坦表面上形成膜,其中一个循环在显示于下表2(工艺循环)中的条件下使用图1A中所说明的PEALD设备和图1B中所说明的气体供应系统(FPS)进行。运载/稀释气体用作等离子体产生气体。沉积具有不同厚度的多种膜用于分析(参见表3)。分析所沉积膜并且展现显示于下表3中的特性。
表2(数值是近似的)
在上文中,GPC在GESA中较低,表明存在本公开中所描述的蚀刻/溅镀作用。
表3(数值是近似的)
在表3中,“均一性(49pt Hi/Lo var%)”表示在衬底的49个点处测量的膜的厚度均一性,表述为最高厚度与最低厚度之间的差异(%);“R.I@633nm”表示当使用波长为633nm的光时的反射性指数;“Dep速率”表示生长速率/循环;“K值@1.5K”表示1.5开尔文(Kelvin)下的介电常数;“J@2MV/cm”表示2MV/cm下的泄漏电流;“BV@10E-3A/cm2(THK6nm)”表示10E-3A/cm2下的崩溃电压;“密封性限制”表示当暴露于HF时展现密封性的最小厚度(根据在涂布有GESA的SiO膜的HF浸渍后观测到的Δ厚度测量,其中如果Δ厚度是0nm,那么GESA膜被视为密闭的);“浊度”表示用分光光度计测量的浊度值,其指示膜粗糙度;“WER”表示使用0.5到2%HF(稀释的氟化氢)溶液的湿式蚀刻速率;“密度”表示使用质量和X射线反射测量术测量的密度;并且“粗糙度”表示使用X射线反射测量术测量的表面粗糙度。
在上文中,具有18nm厚度的膜的RI和具有3.5nm厚度的膜的RI略微不同。归因于原生氧化物(折射率1.4)的底层的贡献,这可能是度量假影。如从上文显而易见,GESA膜是漏电材料,但具有1nm密封性(通常1.5nm或更小),这在最常规薄膜归因于岛生长行为具有2与5nm之间的密封性的传感中明显较低。此外,GESA膜显示极高的耐化学物质性(通常,WER是零或基本上零nm/秒)。GESA膜的浊度值数和粗糙度指示这种膜相当光滑(通常表面粗糙度小于0.5nm),其优选用于大多数应用。由于GESA膜的以上独特的特性,除拓扑选择性沉积能力之外,GESA膜展现到其之后可以用于平面应用,如超薄蚀刻终止。
此外,使膜经历通过飞行时间弹性回缩检测分析(TOF-ERDA)的组成分析。结果显示于下表4中。如表4中所显示,GESA膜由SiCN构成。
表4
TOF-ERDA | Si | N | C | O | H |
At.% | 13.8±1 | 10.3±1 | 53.8±2 | 1.2±0.3 | 20.8±4 |
此外,使用X射线衍射仪使膜经历结晶度分析。图3是显示GESA膜的X射线衍射概况(2θ/θ方法)的图,显示如由箭头指示的两个峰,其指示GESA膜是非晶形的。
如从上文显而易见,GESA膜是SiCN非晶形膜。尽管取决于应用,但非晶形材料存在显著的优势。举例来说,在图案化(使用间隔物和核心)中,在工艺期间非晶形材料可以避免任何可能的优先蚀刻和分辨率损失(在结晶材料中,某些结晶取向的优先蚀刻是众所周知的现象)。
实例2
除显示于下表5中的条件外,在用于实例1中的条件下沉积GESA膜,以确定GESA的特征。
表5
如表5中所显示,即使当“进料”的持续时间比实例1中长五倍时,GPC(生长速率/循环)仅略微地增加但无显著不同,指示在GESA如典型ALD中,前体通过饱和化学吸附于衬底表面上。尽管通过增加“进料”的持续时间,似乎经化学吸附分子形成具有略微大于单层的厚度的原子层,但由于前体的剂量主要受前体的分压控制,因此“进料”的延长的持续时间对膜形成具有较小影响。然而,当不施加RF功率时,由于不使用反应物,因此膜不沉积。另一方面,当RF功率施加的持续时间比实例1中长3倍时,出人意料地,GPC显著增加(超过50%),指示当施加RF功率更长时间时,在衬底表面发生类CVD沉积,而非简单的自限制ALD沉积,施加RF功率更长时间可以对使用存在于衬底上方的残余前驱气体(GESA使用比通常用于常规PEALD的温度高得多的瓶温度(80℃),使得净化不充分)的类CVD沉积有贡献,但所述理论不限制本发明。因此,GESA具有典型ALD的基础特征,但根本上或在化学上不同于典型ALD。
实例3
通过GESA在用于实例1中的条件下,在SiO2膜覆盖的Si衬底(具有300mm直径和0.7mm厚度)上形成膜,所述衬底具有宽度为约30nm的窄沟槽和宽度为约75nm的宽沟槽,它们具有约70nm的深度。SiO2膜通过PEALD以约13nm的厚度形成于衬底上。
图4是显示沉积于沟槽上的GESA膜的截面视图的STEM(扫描透射电子显微镜)照片。如图4中所显示,GESA膜42沉积于覆盖窄沟槽的SiO2膜41的顶表面上,然而基本上无GESA膜沉积于窄沟槽的侧壁或底部43上。GESA膜在每个顶部表面上的中心处的厚度(最高厚度)是5.95到6.6nm(SiO2膜的厚度是约12nm到13nm)。
图5是显示沉积于沟槽上的GESA膜的截面视图的STEM照片。如图5中所示,GESA膜52沉积于覆盖窄和宽沟槽的SiO2膜51的顶表面上,然而不仅窄沟槽而且宽沟槽的侧壁或底部上基本上无GESA膜沉积(GESA膜在每个顶部表面上的中心处的厚度是约7nm)。
图6是显示沉积于沟槽上的GESA膜的截面视图的STEM照片。如图6中所显示,GESA膜62沉积于覆盖窄和宽沟槽的SiO2膜61的顶表面上,然而不仅窄沟槽而且宽沟槽的侧壁或底部上基本上无GESA膜沉积。GESA膜在每个顶部表面上的中心处的厚度(最高厚度)是8.3到10.8nm(SiO2膜的厚度是约12nm到13nm)。在图6中具有反梯形的沟槽的底部表面显示略微模糊的图像,然而图5中的底部表面不显示这类模糊图像,很可能指示通过将GESA膜于沟槽的顶部表面上的厚度减小某一程度,可以基本上完全抑制膜于底部表面上的沉积。在任何情况下,图4、5和6显示无膜沉积于侧壁和V或U形底部表面上。在非限制性理论中,归因于衬底上方的残余前体分子,归因于抑制侧壁处的离子轰击的各向异性等离子体,并且归因于本公开中所描述的蚀刻/溅镀作用,发生GESA,所述残余前体分子有助于缩短离子的平均自由路径并且抑制底部处的离子轰击,产生CVD的非共形沉积概况。
比较实例
除了瓶温度是60℃以外,在用于实例1中的条件下沉积膜。图7是显示根据这个比较实例的沉积于沟槽上的PEALD膜的截面视图的STEM照片。如图7中所显示,膜不仅沉积于覆盖沟槽的底层71的顶表面上,而且沉积于具有反梯形的沟槽的底层71的底部表面上,但似乎膜于侧壁上的沉积受到限制(在侧壁处观测到仅略微并且部分沉积的膜),指示在某一程度上进行了GESA但未进行完全GESA。沉积于顶表面上的膜72和沉积于底部表面上的膜73的厚度基本上类似于实例1中沉积于顶部表面上的膜的厚度。其证实为了进行完全GESA,需要某一饱和蒸气压(BDEAS的饱和蒸气压在70℃下是30mmHg),即,需要某一剂量的前体。在非限制性理论中,当前体的分压足够低以使其在饱和后完全净化时,基本上无残余前体分子留在衬底上方,这缩短等离子体中所含有的离子的平均自由路径,并且因此离子轰击在沟槽底部处不受抑制,从而在底部形成膜。在这个比较实例中侧壁处形成的膜较薄,这很可能是因为使用了为各向异性等离子体的Ar等离子体。
实例4
通过GESA使用图2中所说明的顺序,在Si衬底(具有300mm直径和0.7mm的厚度并且覆盖有SiO2内衬膜)的平坦表面上形成SiCN膜,其中一个循环在显示于下表6(工艺循环)中的条件下使用图1A中所说明的PEALD设备和图1B中所说明的气体供应系统(FPS)进行。运载/稀释气体用作等离子体产生气体。SiO2膜通过PEALD以约13nm的厚度形成于衬底上。
表6(数值是近似的)
图11是显示沉积于具有沟槽的衬底上的GESA膜的截面视图的STEM照片。如图11中所显示,GESA膜(SiCN)162沉积于覆盖窄和宽沟槽的SiO2膜161的表面上,其中基本上无GESA膜沉积于窄沟槽的侧壁或底部上。另一方面,GESA膜沉积于覆盖有SiO2膜161的沟槽的每个顶部表面上,并且还沉积于宽沟槽的底部和U形底部表面上,但底部上的GESA膜比顶部表面上的GESA膜更薄。为了有效地抑制GESA膜于沟槽的底部上的沉积,沟槽需要窄,例如沟槽的宽度应<50nm(在这种情况下,沟槽的宽度是62nm)。GESA膜在每个顶部表面上的中心处的厚度(最高厚度)是9.7到11.2nm(SiO2膜的厚度是约9nm到10nm),其中在图11中,GESA膜和SiO2膜在每个顶部表面上的中心处的总厚度是19.7nm到20.2nm。GESA膜在宽沟槽的底部表面和U形底部表面处的厚度分别是7nm(SiO2膜的厚度是约9.5nm)和3nm(SiO2膜的厚度是约9nm),其中在图11中,GESA膜和SiO2膜在底部处的总厚度分别是16.2nm和14.1nm。图11显示基本上无GESA膜沉积于侧壁和V形底部表面上。
然后,在同一腔室中在显示于下表7中的条件下,将以与上文所描述相同的方式获得的具有覆盖有GESA膜的沟槽的衬底暴露于氧气等离子体。
表7(数值是近似的)
图12是显示暴露于氧气等离子体时GESA膜的截面视图的STEM照片。如图12中所显示,GESA膜(SiCN)162与SiO2膜161之间的区别或对比基本上消失,形成整合的单氧化物膜163,即,通过STEM未观测到其间的边界,指示SiCN有效地转化成SiO(无碳)(尽管理论上其间的区别可以使用与电子能量损失谱分析(Electron Energy Loss Spectroscopy,EELS)连接的高分辨率透射电子显微镜(High-Resolution Transmission ElectronMicroscopy,HR-TEM)检测)。
同样,如图12中所显示,GESA膜通过暴露于氧气等离子体而在某一程度上被蚀刻(约50%,通常10%到70%),所述氧气等离子体由于等离子体的蚀刻/溅镀作用而修整或蚀刻GESA膜。
实例5和6
通过GESA在SiO内衬覆盖的衬底上以基本上类似于实例4中的方式沉积SiCN膜,并且接着除了实例5中RF功率是400W并且实例6中是100W以外,以基本上类似于实例4中的方式将GESA膜沉积的衬底暴露于氧气等离子体。
图13显示在暴露于氧气等离子体之前(GESA POR)、在实例5中在使用100W RF功率暴露于氧气等离子体时(TS-SiO 100W)、并且在实例6中在使用400W RF功率暴露于氧气等离子体时(TS-SiO 400W)的GESA膜的XPC光谱(x轴表示键结能量eV)。如图13中所显示,在暴露于氧气等离子体后,GESA膜(SiCN)有效地转化成SiO膜,其中使用100W RF功率和400W RF功率获得的两种膜清晰地显示出Si-O-Si键的形成以及Si-N键和Si-H键的解离,并且当RF功率更高时以上趋势更明显。此外,使每种膜经历通过飞行时间弹性回缩检测分析(TOF-ERDA)的组成分析。结果显示于下表8中。如表8中所显示,GESA膜(SiCN)转化成SiO膜,其中碳和氮均未检测到(即,小于可检测水平),然而检测到了高水平的Si和O。
表8
此外,分析每种膜并且展现显示于下表9中的湿式蚀刻特性。
表9
GESA_SiO_100W | GESA_SiO_400W | GESA_POR | |
WERR(TOX) | 7.9 | 2.1 | 0 |
“WERR(TOX)”表示相对于热氧化物膜使用0.5到2%HF(稀释的氟化氢)溶液的湿式蚀刻速率。
如上文所描述,通过将GESA-SiCN膜暴露于氧气等离子体,所述膜可以转化成SiO膜,并且SiO质量或特性可以根据氧气等离子体的强度来调整。
实例7
通过GESA使用图2中所说明的顺序,在表面提供有EUV光致抗蚀剂图案的Si衬底(具有300mm直径和0.7mm厚度)上形成SiN膜,其中一个循环在显示于下表10(工艺循环)中的条件下使用图1A中所说明的PEALD设备和图1B中所说明的气体供应系统(FPS)进行。运载/稀释气体用作等离子体产生气体。通过EUV激光光刻形成EUV光致抗蚀剂图案,所述图案具有约20nm的宽度,约35nm的高度和约40nm的间距。
表10(数值是近似的)
通过GESA使用N2等离子体沉积于光致抗蚀剂图案上的SiN膜的横截面视图的STEM照片(未显示)证实GESA膜占优势地沉积于抗蚀剂的顶部表面上,其中GESA膜在顶部表面上的中心处具有约7nm的厚度(最高厚度),在沟槽的底部表面的中心处具有约3.7nm的厚度(最高厚度),并且在侧壁的大致中点处具有约2.7nm的厚度,并且GESA膜和抗蚀剂在中心处的总高度是约40nm,并且GESA膜和抗蚀剂在侧壁的大致中点处的总宽度是约22nm。
此外,使膜经历通过飞行时间弹性回缩检测分析(TOF-ERDA)的组成分析。结果显示于下表11中。如表4中所显示,GESA膜由SiCN构成。
表11(数值是近似的)
在上文中,“GESA(POR)”是指使用氩气等离子体的有规律的GESA膜。如表11中所显示,通过使用氮气等离子体替代氩气等离子体,SiN膜被有效地沉积(不含有可检测的氧和碳)。
如上文所描述,通过将GESA膜直接沉积于光致抗蚀剂图案上,抗蚀剂的强度可以增加(特别地,EUV光致抗蚀剂似乎较弱),并且抗蚀剂的高度可以增加,使得图案转移分辨率可以得到改良。
所属领域的技术人员应理解,可以在不脱离本发明的精神的情况下进行大量和各种修改。因此,应明确理解,本发明的形式仅是说明性的,并且并不打算限制本发明的范围。
Claims (20)
1.一种拓扑实现选择性沉积(topology-enabling selective deposition)的方法,其中在半导体制造中,膜选择性沉积于具有由底部和侧壁构成的凹槽图案的衬底的顶部表面上,所述方法依序包含:
(i)将前体供应到所述衬底放置在电极之间的反应空间,所述前体除金属或类金属原子以外含有包括碳和/或和卤化物的多种元素;
(ii)净化所述反应空间,仅达到与化学吸附于所述衬底的所述顶部表面上的前体的量相比更大量的前体保留在所述衬底的所述顶部表面附近的程度;和
(iii)在所述电极之间施加RF功率,同时供应基本上不含H和O的等离子体产生气体,以产生所述衬底暴露于其的富离子各向异性等离子体,由此将拓扑限制层选择性并占优势地沉积于所述衬底的所述顶部表面上,其中基本上无层或基本上比所述拓扑限制层更薄的层沉积于所述凹槽图案的所述侧壁和所述底部上。
2.根据权利要求1所述的方法,其中所述前体含有硅或金属、碳、氮和氢。
3.根据权利要求1所述的方法,其中在步骤(i)中,在不在所述电极之间施加RF功率的情况下,使用运载气体通过含有呈液体状态的所述前体的瓶,将所述前体供应到所述反应空间,其中所述瓶中的蒸气压是约30mmHg或更高。
4.根据权利要求2所述的方法,其中所述拓扑限制层由以下构成:SiCN、SiN、TiCN、TiN、ZrCN、ZrN、HfCN、HfN、TaCN、TaN、NbCN、NbN、AlCN、AlN、CoCN、CoN、CuCN、CuN、WCN、WN、RuCN、RuN、NiCN、NiN LaCN、LaN、TiNCl、HFNCl或WFN。
5.根据权利要求1所述的方法,其中贯穿所述沉积步骤除所述等离子体产生气体以外无反应物供应到所述反应空间。
6.根据权利要求1所述的方法,其中所述凹槽图案的宽度小于100nm。
7.根据权利要求1所述的方法,其中在步骤(i)中,在不在所述电极之间施加RF功率的情况下将所述前体供应到所述反应空间,并且所述方法进一步包含(iv)在步骤(ii)之后立即净化反应室,其中仅重复步骤(i)到(iv)直到所述拓扑限制层的厚度达到1nm到100nm。
8.根据权利要求1所述的方法,其中所述运载气体和/或稀释气体是Ar、He和/或N2。
9.根据权利要求1所述的方法,其中所述凹槽图案是由间隔地布置于模板上的光致抗蚀剂线或垂直间隔物构成的图案,并且在步骤(iii)中,
所述拓扑限制层作为伞层选择性并占优势地沉积于每一光致抗蚀剂线或每一垂直间隔物的顶部表面上,其中基本上无层或基本上比所述拓扑限制层更薄的层沉积于所述光致抗蚀剂线或所述垂直间隔物的侧壁上和所述模板的暴露表面上,随后通过各向异性蚀刻使用具有所述伞层的所述光致抗蚀剂线或所述垂直间隔物,将由所述光致抗蚀剂线或所述垂直间隔物构成的所述图案转移到所述模板。
10.根据权利要求9所述的方法,其中所述拓扑限制层沉积于由氧化硅或金属氧化物制成的所述垂直间隔物上,并且通过间隔物界定双图案化(SDDP)产生。
11.根据权利要求9所述的方法,其中所述拓扑限制层沉积于通过EUV光刻形成的所述光致抗蚀剂线上。
12.根据权利要求9所述的方法,其中所述伞层的厚度在1nm到15nm范围内。
13.根据权利要求1所述的方法,其中所述凹槽图案是由FinFET装置的fin结构构成的图案,并且在步骤(iii)中,
所述拓扑限制层作为保护层选择性并占优势地沉积于由氧化硅或金属氧化物制成的每个fin结构的顶部表面上,其中基本上无层或基本上比所述拓扑限制层更薄的层沉积于所述fin结构的侧壁上和所述衬底的暴露表面上。
14.根据权利要求1所述的方法,在步骤(iii)后进一步包含(v)在所述反应空间中将步骤(iii)中获得的所述拓扑限制层暴露于氧气等离子体,以将为基于氮化物的层或碳氮化物层的所述拓扑限制层转化成基于氧化物的层。
15.根据权利要求14所述的方法,其中所述拓扑限制层沉积于基于氧化物的底层上,其中在步骤(v)中所述拓扑限制层完全转化成所述基于氧化物的层,使得所述拓扑限制层与所述底层之间基本上不存在能够检测的接缝。
16.根据权利要求15所述的方法,其中形成于所述基于氧化物的底层上的所述拓扑限制层的厚度通过步骤(v)中的所述氧气等离子体处理而减小。
17.根据权利要求14所述的方法,其中步骤(v)在重复步骤(i)到(iii)的每一预设次数后进行。
18.根据权利要求17所述的方法,其中所述拓扑限制层的厚度在完成步骤(v)时大于20nm。
19.根据权利要求14所述的方法,其中步骤(v)在完成步骤(i)到(iii)后作为沉积后处理而进行。
20.根据权利要求19所述的方法,其中所述拓扑限制层的厚度在步骤(v)时在5nm到20nm范围内。
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US10340135B2 (en) | 2019-07-02 |
CN108122739B (zh) | 2023-07-21 |
US20180151346A1 (en) | 2018-05-31 |
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