CN112670156A - 氧化硅的拓扑选择性膜形成的方法 - Google Patents
氧化硅的拓扑选择性膜形成的方法 Download PDFInfo
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- CN112670156A CN112670156A CN202011082907.9A CN202011082907A CN112670156A CN 112670156 A CN112670156 A CN 112670156A CN 202011082907 A CN202011082907 A CN 202011082907A CN 112670156 A CN112670156 A CN 112670156A
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- silicon nitride
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- 238000000034 method Methods 0.000 title claims abstract description 207
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 70
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- 239000000758 substrate Substances 0.000 claims abstract description 78
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 77
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000000151 deposition Methods 0.000 claims abstract description 72
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- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 4
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- 238000009825 accumulation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- AIHCVGFMFDEUMO-UHFFFAOYSA-N diiodosilane Chemical compound I[SiH2]I AIHCVGFMFDEUMO-UHFFFAOYSA-N 0.000 description 1
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- 230000000149 penetrating effect Effects 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 238000012876 topography Methods 0.000 description 1
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
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Abstract
一种用于在衬底上形成的阶梯上形成氧化硅膜的方法,其包含:(a)通过预先选择初始氮化硅膜的目标部分,参照初始氮化硅膜的非目标部分,选择性地沉积或去除或重整产生最终氧化硅膜来设计最终氧化硅膜的拓扑结构;和(b)根据工艺(a)中设计的拓扑结构在阶梯的表面上形成初始氮化硅膜和最终氧化硅膜,其中初始氮化硅膜使用含卤素的含硅前体通过ALD来沉积,并且通过氧化初始氮化硅膜将初始氮化硅膜转化为最终氧化硅膜,而不进一步沉积膜,其中初始氮化硅膜中的Si‑N键转化为Si‑O键。
Description
技术领域
本发明大体上涉及一种在衬底上形成的具有顶面、侧壁和底面的阶梯上形成氧化硅膜的方法,特别是氧化硅的拓扑选择性膜形成的方法。
背景技术
原子层沉积(ALD)方法,包括等离子体增强原子层沉积(PEALD)方法,作为在具有图案化表面的衬底上形成保形膜的方法被广泛用于半导体制造工艺中。在一些半导体制造工艺中,对已经形成为保形膜一次的膜进行干法蚀刻或其他干法修整工艺,以便各向异性地去除膜的一个或多个部分以用于特定应用。在这种情况下,膜形成工艺和蚀刻工艺必然分两个步骤进行。
然而,在对薄膜进行蚀刻时,薄膜、底层膜和掩膜材料的蚀刻选择性,即薄膜、底层膜和掩膜材料之间的抗蚀刻性存在一定程度的差异始终是一个问题,并且例如对底层膜的不利影响(例如,穿透离子能量使底层膜的质量下降,沟槽的临界尺寸(CD)下降)是不可避免的。
如果膜形成本身可以通过各向异性沉积和/或各向异性重整工艺控制膜的拓扑结构,则不需要干法蚀刻或其他干法修整工艺,从而消除干法蚀刻对底层膜的不利影响,减少工艺步骤的数目,并提高产量。然而,控制氧化硅膜的拓扑结构是非常困难的,因为在膜沉积工艺中,氧化是相当各向异性地发生的。
作为这种控制膜拓扑结构的技术,众所周知,首先在一定条件下将SiN膜沉积在衬底的图案化表面上,使图案的水平部分和竖直部分的湿法蚀刻速率不同,然后进行湿法蚀刻,从而选择性地仅留下图案的侧壁部分或图案的水平部分(如例如美国专利公开号2017/0243734中所公开,其公开内容在适用于本文公开的某些实施例时以全文引用的方式并入本文中)。该技术可被称为SiN的拓扑选择性膜形成(“TS-SiN”)。在上文中,由于使用湿法蚀刻而非干法蚀刻来选择性地仅去除图案的竖直或水平部分,故可以相对于底层膜设置图案的高湿法蚀刻选择性,并实现不需要考虑蚀刻的均匀性的优点。在TS-SiN中,高湿法蚀刻选择性可通过提高RF功率获得;然而,这样的条件不适用于在SiO膜上赋予类似的高湿法蚀刻选择性。因此,虽然半导体工业中对SiO的拓扑选择性膜形成(“TS-SiO”)有着高的需求,但尚未成功实现TS-SiO。
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
在一些实施例中,通过首先将SiN膜选择性地沉积在衬底的阶梯中所沉积的SiO膜的水平表面上,在衬底的阶梯中形成拓扑选择性SiO(TS-SiO)膜,其中水平表面(阶梯的顶面和底面)主要是通过将SiO膜暴露于具有相对高离子能量的含NH3或N2/H2的等离子体中,由各向异性等离子体进行选择性处理(该表面处理可称为“温育”或“表面氮化”),随后使用含卤素的前体主要选择性地在阶梯的水平表面上对SiN膜进行PEALD(该沉积工艺可称为“氮化”),其中吸附在衬底表面的前体被氮化,其中前体中的卤素通过交换反应(例如Si-Cl→Si-N)用氮化气体中的氮替换,从而形成SiN的单层。作为第二工艺,通过氧化处理(该处理可称为“氧化(oxidization/oxidation)”)将沉积的SiN膜转化为SiO膜,从而使所得膜的主要成分是SiO,由于在将膜转化为SiO膜时可以重复进行各向异性的氮化处理,因此所得膜可以仅在竖直方向上生长或主要在竖直方向上生长,从而可以实现各向异性的PEALD。
各向异性氮化或选择性氮化是通过各向异性或选择性温育或表面氮化来实现的,其各向异性现象是由于含氮等离子体的各向异性离子的入射。为了处理SiO表面,需要超过一定水平的离子能量,因此,各向异性表面处理可以基本上仅在或主要在暴露于离子能量的SiO膜的一部分实现,从而在表面引入-NH端基。另一方面,当氧化SiN膜时,可以在没有离子能量辅助的情况下通过等离子体容易地进行氧化,即氧化处理可以在图案化结构上均匀地完成。
当图案化结构具有高纵横比和窄开口的沟槽时,注入沟槽内部的离子数量比辐射到顶面的离子数量少。因此,与顶面相比,沟槽内部不会发生氮化。通过利用上述现象,当图案具有窄开口时,可以选择性地并且主要仅在顶面形成SiO膜。适合于上述操作的纵横比和开口尺寸的可工作范围根据沉积条件如沉积压力和RF功率而变化。
在沉积SiN膜的底层SiO膜的表面上,通过各向异性或选择性温育或表面氮化形成-NH端基。作为沉积SiN膜的前体,可以使用任何能够吸附在具有暴露的Si-NH表面的底层SiO膜上但几乎不吸附在Si-O表面上的前体,例如SiCl4、Si2Cl6等。
在通过氧化处理将SiN膜转化为SiO膜后,根据需要,可以使用例如dHF对图案化结构进行湿法蚀刻,以便可以去除任何作为残余物残留在侧壁上的SiO膜,从而形成完整的TS-SiO膜。虽然原则上SiN膜仅沉积在顶面,但沉积SiN膜的前体的表面选择性,即选择性地沉积在Si-NH表面而不是Si-O表面上,可能并不完美。在这种情况下,SiN膜可能会稍微沉积在侧壁上,由于氧化是各向异性发生的,所以会转化为SiO膜。通过对图案化结构进行湿法蚀刻,可以去除侧壁上残留的SiO膜。应注意,参照热氧化物膜的湿法蚀刻速率为1,SiO膜的湿法蚀刻速率为约2.2,与位置无关,即SiO膜的顶部部分的湿法蚀刻速率、SiO膜的侧壁部分的湿法蚀刻速率和SiO膜的底部部分的湿法蚀刻速率基本上或大部分相等。因此,虽然湿法蚀刻不仅蚀刻SiO膜的侧壁部分,而且蚀刻SiO膜的顶部部分,但由于SiO膜的顶部部分主要或基本上比其侧壁部分厚,因此可以获得完整的TS-SiO膜。
在一些实施例中,用于沉积SiN膜的前体不含碳,并且最终的氧化硅膜不含碳,据此可以避免包括从SiN膜迁移到SiN膜和底层膜之间的界面的碳在内的杂质的分散。在将SiN膜转化为SiO膜后,可以形成同样不含碳的SiO膜。通过形成无碳的SiO膜,可以避免任何由SiO膜迁移的杂质如碳通过SiO膜与底层膜之间的界面进入底层膜而导致底层膜质量下降。
一些实施例的特征在于使用含卤素的无机无碳前体以及无碳反应剂。常规上,当使用含卤素的前体时,借助反应剂进行沉积,该反应剂是含氮的烃(直链或环状),例如吡啶,其中氮通过交换反应(例如)替换吸附在衬底上的前体中与硅(例如Cl-Si)键合的卤素,从而形成由SiN材料构成的膜。然而,由于反应剂化合物中含有烃,因此膜中残留一些碳的可能性是不可忽视的。另外,在某些情况下,前体含有烃。通过使用含卤素的无机无碳前体和无碳反应剂,可以通过PEALD沉积无碳SiN膜,然后进行转化工艺,其中SiN膜通过氧化处理转化为SiO膜。
当重复上述工艺以形成具有所需厚度的SiO膜时,如果无碳前体在SiO表面上的吸附不足,导致每循环生长(GPC)降低和/或阶梯覆盖率降低,则在沉积SiN膜的工艺之前(即在馈送前体之前),可将SiO表面暴露于NH3、N2/H2等的等离子体中,以改善前体在衬底表面上的吸附。
拓扑选择性处理技术不限于上述实施例。拓扑选择性处理技术是一种基本上将使用含卤素的含硅前体通过PEALD形成氮化物膜与氮化物膜氧化组合的技术,在一些实施例中包括以下三种技术:
1)通过ALD或CVD在图案化衬底上沉积薄的SiO膜,然后通过操纵或调整RF功率,使用含卤素前体通过PEALD沉积SiN膜,其中由于各向异性温育或表面氮化工艺,SiN膜选择性地生长在图案化衬底的水平面,特别是顶面,其中水平面比竖直面接收更多的离子能量,并且表面氮化基本上仅发生在或主要发生在水平面,而不是竖直面;
2)使用含卤素的前体通过ALD(热或等离子体增强)在图案化衬底上沉积SiN膜,然后在等离子体能、UV光能、热能或其他能量的辅助下,使用氧化材料如O2将SiN膜转化为SiO膜,然后进行湿法蚀刻,其中通过施加100至1,000W的RF功率五秒或更短的时间来沉积SiN膜,使沉积在侧壁上的膜的一部分的氮化变得不完全,并且该部分对湿法蚀刻的抗性变得不足,从而通过湿法蚀刻去除侧壁上的膜的一部分,并留下沉积在水平面上的膜的一部分;以及
3)在上述2)中,通过在沉积SiN膜时施加100至1,000W的RF功率大于五秒,可以使沉积在顶面的膜的一部分、沉积在侧壁的膜的一部分和沉积在底面的膜的一部分之间的膜特性如湿法蚀刻抗性基本上相等,由此,在湿法蚀刻后,可以形成保形SiO膜(无碳)。在本公开中,虽然标明了300mm衬底的RF功率,但当RF功率用于具有不同直径的衬底时,可以通过计算衬底的单位面积的瓦数(W/cm2)来确定适用于该衬底的RF功率。
在一些实施例中,前体选自无碳、含卤素的基于硅烷的化合物,并且反应剂(氮化气体)选自N2/H2、NH3或其它NxHy(x和y不为零)中的至少一种。
在一些实施例中,无碳、含卤素的基于硅烷的化合物包括但不限于二碘硅烷、二氯硅烷、六氯二硅烷和八氯三硅烷,其可以单独使用或以前述两种或多种的任何组合使用。
在一些实施例中,氮化(通过交换反应用氮替换卤素)和氧化在同一反应室中依次连续进行,其中在氮化后,使用惰性气体对反应室进行吹扫,然后,将O2、O3、CO2、N2O、H2O等氧化气体或前述两种或更多种的组合馈送到反应室中并进行氧化,从而形成SiO膜。
在一些实施例中,氮化和氧化不需要重复相同的次数,但通过调整和改变氮化和氧化的重复次数以及调整RF功率,可以降低膜的湿法蚀刻抗性(例如,通过增加氧化的重复次数、降低氮化的RF功率和/或增加氧化的RF功率)。
在一些实施例中,通过调整在顶面、侧壁和底面上形成的膜的湿法蚀刻抗性(湿法蚀刻速率),可以通过湿法蚀刻(例如使用dHF)选择性地去除或保持顶面、侧壁和底面的各自部分。
在一些实施例中,当通过PEALD进行氮化和氧化时,有时,前体在衬底表面上的吸附程度在氧化时变低,在这种情况下,通过在氧化时使用如H2、NH3等含氢的还原气体改善衬底的表面条件,可以改善含卤素前体的吸附特性,从而提高每循环生长(GPC)。
在本公开中,除非另外说明,否则SiN、SiO、SiOC等是以非化学计量的方式表示膜类型的缩写。
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。
本发明的其它方面、特征和优势将从之后的详细描述变得显而易见。
附图说明
现将参照优选实施例的附图来描述本发明的这些和其他特征,这些优选实施例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为可用于本发明的一个实施例中的用于沉积保护膜的PEALD(等离子体增强原子层沉积)装置的示意图。
图1B示出了可用于本发明的一个实施例中的使用流通系统(FPS)的前体供应系统的示意图。
图2为流程图,示出了根据本发明的一个实施例的拓扑选择性膜形成的工艺。
图3为流程图,示出了根据本发明的另一个实施例的拓扑选择性膜形成的工艺。
图4为流程图,示出了根据本发明的另一个实施例的拓扑选择性膜形成的工艺。
图5为流程图,示出了根据本发明的另一个实施例的拓扑选择性膜形成的工艺。
图6为示出根据本发明的一个实施例的拓扑选择性膜形成的工艺顺序的时序图,其中每一列的宽度不一定表示实际时长,每一行中的线的抬高表示开启状态,而每一行中的线的下沉表示关闭状态。
图7为示出根据本发明的另一个实施例的拓扑选择性膜形成的工艺顺序的图,其中灰色的单元格表示开启状态,而白色的单元格表示关闭状态,并且每一列的宽度不代表每个工艺的持续时间。
图8为示出膜形成的常规工艺的顺序的图,其中灰色的单元格表示开启状态,而白色的单元格表示关闭状态,并且每一列的宽度不代表每个工艺的持续时间。
图9示出了显示根据本发明的一个实施例的拓扑选择性膜形成工艺的示意图截面视图。
图10示出了显示根据本发明的另一个实施例的拓扑选择性膜形成工艺的示意图截面视图。
图11示出了显示根据本发明的另一个实施例的拓扑选择性膜形成工艺的示意图截面视图。
具体实施方式
在本公开中,“气体”可包括气化的固体和/或液体并可由单一气体或气体的混合物构成。在本公开中,通过喷头引入到反应室中的工艺气体可以包含前体气体和添加剂气体、基本上由其组成或由其组成。前体气体和添加剂气体通常以混合气体形式或单独地引入到反应空间中。前体气体可以用运载气体,如稀有气体加以引入。添加剂气体可以包含反应气体和如稀有气体的稀释气体、基本上由其组成或由其组成。反应气体和稀释气体可以以混合气体形式或单独地引入到反应空间中。前体可以包含两种或更多种前体,并且反应气体可以包含两种或更多种反应气体。前体是化学吸附在衬底上并且通常含有构成介电膜基质主要结构的类金属或金属元素的气体,并且用于沉积的反应气体是当气体被激发时与化学吸附在衬底上的前体反应以将原子层或单层固定在衬底上的气体。“化学吸附”是指化学饱和吸附,也可以简单地称为“吸附”。除过程气体之外的气体,即,不穿过喷淋头引入的气体,可以用于例如密封反应空间,该气体包括密封气体,诸如稀有气体。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以覆盖整个目标或相关表面的基本上无小孔的层,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。
在本公开中,“含有Si-O键”可指通过一个或多个Si-O键表征、具有基本上由一个或多个Si-O键构成的主骨架、和/或具有基本上由一个或多个Si-O键构成的取代基。含有Si-O键的介电膜包括但不限于具有约2至10、通常约4至8的介电常数的SiO膜、SiOC膜和SiON膜。
此外,在本公开中,除非另外指明,否则冠词“一个”或“一种”是指某个种或包括多个种的某个属。在一些实施例中,术语“由……构成”和“具有”独立地指“通常或广泛地包含”、“包含”、“基本上由……组成”或“由……组成”。另外,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。
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都可以构成所述变量的可工作范围,并且所指示的任何范围都可以包括或排除端点。另外,任何所指示的变量值(无论它们是否用“约”指示)都可指精确值或近似值并包括等效值,并且在一些实施例中可指平均值、中位数、代表性值、多数值等。
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。在所有公开的实施例中,出于预定目的,在一个实施例中所用的任何要素都可以用与其等效的任何要素替代,包含本文中明确地、必要地或内在地公开的那些要素。此外,本发明可同等地适用于设备和方法。
将参照优选实施例来阐述实施例。然而,本发明不限于所述优选实施例。
一个例示性实施例涉及基于PEALD技术的介电膜形成工艺,其中通过使用等离子体的各向异性表面处理对图案化模板的基本上仅或主要是水平的面进行表面处理,然后在表面处理过的面上选择性地生长膜。膜的生长主要在竖直方向上发生,而抑制水平方向上的膜生长,从而获得具有所需拓扑结构的膜轮廓。通过这种技术,在衬底的顶面和衬底的凹槽的侧壁之间,可以基本上仅在衬底的顶面上沉积膜。术语“基本上仅”是指例如总量的70%、80%、90%或95%或更高,例如,沉积在顶面上的膜的一部分的平均厚度与沉积在侧壁上的膜的一部分的平均厚度之比为7/3或更高。
例如,尽管底面也是水平面,但是底面上的膜形成程度取决于纵横比。如果沟槽的纵横比高,例如当开口尺寸为50nm或更小时,为3或更高,则与暴露于离子轰击的顶面相比,进入沟槽的离子数量变得很低。因此,通过表面处理(SiO表面的氮化处理)的表面氮化或温育在底面上的进展不如在顶面上的进展,因此,在底面上生长的膜的厚度比在顶面上生长的膜的厚度小。通过调整凹槽的纵横比,例如使用纵横比为10或更高的凹槽,在顶面、侧壁、底面之间,可以基本上在顶面上沉积膜。
在一些实施例中,拓扑选择性工艺包含:A)使用等离子体以基本上仅处理图案化衬底的水平面的方式进行各向异性表面处理(温育或表面氮化);B)使用含有卤素活性基团的前体和NH3、N2/H2等的等离子体,通过PEALD在表面处理面上沉积氮化物膜(通过卤素和氮之间的交换反应进行氮化);C)通过在吹扫反应室之后通入例如O2,将反应室中的气体改变为氧化性气氛,并通过例如热氧化、自由基氧化、等离子体氧化等使氮化物膜氧化,从而将氮化物膜转化为氧化物膜;以及D)重复步骤A)至C),直到氧化物膜的厚度达到所需的值,其中氧化物膜具有所需的拓扑选择性膜轮廓。
在一些实施例中,氧化物膜由SiO、SiOC、SiON等构成。由于进行了各向异性的表面处理,所以膜基本上仅在竖直方向上生长,而不在水平方向上生长。通过使用具有高纵横比的凹槽,在顶面、侧壁和底面之间,可以基本上仅在顶面形成膜。此外,根据需要,通过对最终沉积的氧化物膜进行各向同性湿法蚀刻(例如,使用dHF),可以完全去除侧壁上的膜,从而形成仅顶面和底面上的膜可以保留的膜轮廓。此外,在一些实施例中,表面处理和沉积工艺可以使用同一反应室连续进行。
在拓扑选择性处理技术中,通过使用无碳前体和无碳氮化反应剂如N2、N2/H2、NH3等沉积SiN膜,然后,通过氧化交换反应使用如O2、H2O等氧化气体将SiN膜氧化而将SiN膜转化为SiO膜,可以形成在衬底上生长的无碳SiO膜。通过这种技术,在进行SiO膜的形成的同时,可以抑制包含在工艺气体(包括前体和反应剂)中的杂质在SiO膜和底层膜之间的界面上的积累。
一些实施例提供了一种用于在衬底上形成的具有顶面、侧壁和底面的阶梯上形成氧化硅膜的方法,其包含以下工艺:(a)设计最终氧化硅膜的拓扑结构,所述最终氧化硅膜是保形膜或具有低保形性的膜,通过预先选择初始氮化硅膜的目标部分,参照初始氮化硅膜的非目标部分,选择性地沉积或去除或重整产生最终氧化硅膜而在阶梯上形成,所述选择性沉积的目标部分是形成在阶梯的顶面和底面的初始氮化硅膜的顶部/底部部分,所述选择性去除或重整的目标部分是形成在阶梯的侧壁上的初始氮化硅膜的侧壁部分;和(b)根据工艺(a)中设计的拓扑结构在阶梯的表面上形成初始氮化硅膜和最终氧化硅膜,其中初始氮化硅膜使用含卤素的含硅前体通过原子层沉积(ALD)来沉积,初始氮化硅膜通过氧化初始氮化硅膜转化为最终氧化硅膜,而不进一步沉积膜,其中初始氮化硅膜中的Si-N键转化为Si-O键。图2是表示上述拓扑选择性膜形成工艺的流程图。如图2所示,有三种技术交替使用或任意组合使用,以实现最终氧化物膜的所需拓扑结构:选择性地沉积膜的目标部分,选择性地去除膜的目标部分,以及选择性地重整膜的目标部分。
在本公开中,术语“阶梯”或“凹槽”是指由相对于在衬底中形成的参考平面(底面)的立板(侧壁)和踏板(顶面)构成的任何图案化结构,并且在一些实施例中,阶梯可以是具有约10至约50nm(通常约15至约30nm)宽度的沟槽(其中当沟槽的长度与宽度基本上相同时,它被称为孔/通孔,其直径为约10至约50nm)、约30至约200nm(通常约50至约150nm)的深度,以及约3至约20(通常约3至约10)的长宽比。在一些实施例中,最终氧化硅膜选择性地形成在顶面(具有约0至约10%、约20%或约30%或更低的保形性)或沿着衬底的阶梯或沟槽均匀地形成(具有约70%至约110%的保形性,典型地约80%或更高,更典型地约90%或更高,以及100%或更低),其中“保形性”是通过比较在凹槽的侧壁或底面的某个点(通常是横截面视图中的中间点)上形成的膜厚度和在凹槽外的平面(顶面)上形成的膜厚度来确定的。
在一些实施例中,工艺(b)中使用的前体不含碳,并且最终氧化硅膜不含碳。
在一些实施例中,初始氮化硅膜的形成(其可称为“氮化”,其中反应剂的氮通过交换反应替代被吸收的前体的卤素)和初始氮化硅膜的氧化在工艺(b)中在同一反应空间中连续进行。在一些实施例中,在初始氮化硅膜形成后,在初始氮化硅膜氧化前对反应空间进行吹扫,初始氮化硅膜的氧化是在引入氧化气体的反应空间中进行的等离子体氧化,所述氧化气体是选自由O2、O3、CO2、N2O和H2O组成的组中的至少一种气体。在本公开中,“连续”是指不打破真空,不随时间线中断,不改变处理条件,紧随其后,作为下一步,或者在一些实施例中两个结构之间没有离散的物理或化学边界。氮化通常要求基本上完成,因为氮化物膜中的任何剩余卤素可被视为杂质,如碳,它可能迁移到氮化物膜和底层膜之间的界面。
在一些实施例中,初始氮化硅膜由多个单层构成,并且在工艺(b)中,初始氮化硅膜的氧化在初始氮化硅膜的ALD的每个单层沉积循环之后或在初始氮化硅膜的ALD的每多个单层沉积循环之后进行。
在一些实施例中,工艺(a)中预先选择的目标部分是选择性沉积的目标部分,其中工艺(b)包含:(ci)在衬底上的阶梯表面上沉积氧化硅膜;(cii)将衬底与两个电极平行地放置在所述两个电极之间,以主要在阶梯的顶面和底面而不是在阶梯的侧壁上氮化氧化硅膜表面的方式,使用在两个电极之间施加RF功率产生的含氮氢等离子体对氧化硅膜的表面进行各向异性氮化,从而
在氧化硅膜的表面上引入-NH端基;(ciii)使用前体和由在两个电极之间施加RF功率产生的等离子体激发的氮化气体,通过ALD在经过表面处理的氧化硅膜上沉积初始氮化硅膜的至少一部分并与之接触;(civ)使用激发的氧化气体对初始氮化硅膜的至少一部分进行氧化,以获得最终氧化硅膜的至少一部分,而不进一步沉积膜,其中初始氮化硅膜中的Si-N键转化为Si-O键;以及(cv)根据需要,重复工艺(cii)和(civ),直到获得具有所需厚度的最终氧化硅膜。图3是表示上述拓扑选择性膜形成工艺的流程图。
在一些实施例中,工艺(cii)中的含氮氢等离子体使用N2和H2的混合物、NH3、其它NxHy生成,其中x和y为整数,或使用前述两种或更多种的混合物生成。
在一些实施例中,工艺(ci)中的氧化硅膜通过ALD或CVD沉积。
在一些实施例中,工艺(a)中预先选择的目标部分是选择性去除的目标部分,其中工艺(b)包含:(di)使用前体和由在两个电极之间施加RF功率产生的等离子体激发的反应气体,通过ALD在衬底上的阶梯的表面上沉积初始氮化硅膜的至少一部分,所述衬底与两个电极平行地放置在所述两个电极之间,其中在ALD的每个单层沉积循环中,RF功率以每单位面积衬底0.14W/cm2至1.41W/cm2施加五秒或更短的时间,从而使目标部分比非目标部分在进行湿法蚀刻时具有更低的耐化学性;(dii)使用激发的氧化气体对初始氮化硅膜的至少一部分进行氧化,以获得中间氧化硅膜的至少一部分,而不进一步沉积膜,其中初始氮化硅膜中的Si-N键转化为Si-O键;以及(diii)根据需要,重复工艺(di)和(dii),直到获得具有所需厚度的中间氧化硅膜;然后(div)湿法蚀刻中间氧化硅膜,以获得最终的介电膜,从而参照非目标部分主要去除目标部分。图4是表示上述拓扑选择性膜形成工艺的流程图。
在一些实施例中,工艺(dii)中的氧化使用等离子体、UV光、热或前述两种或更多种的组合进行。
在一些实施例中,工艺(di)中使用的RF功率为每单位面积衬底0.14W/cm2至0.71W/cm2,并且工艺(dii)中的氧化是在工艺(di)中初始氮化硅膜的ALD的每个单层沉积循环后或初始氮化硅膜的ALD的每多个单层沉积循环后进行的等离子体氧化,其中等离子体是通过在两个电极之间施加每单位面积衬底0.07W/cm2至0.71W/cm2的RF功率而产生,所述衬底与两个电极平行地放置在所述两个电极之间。
在一些实施例中,进行工艺(diii),其中在每次即将重复工艺(di)之前,将衬底的阶梯的表面暴露于含氢还原气体,以用含氢还原气体处理表面。
在一些实施例中,含氢还原气体是选自由H2和NH3组成的组的至少一种气体。
在一些实施例中,在工艺(div)中,湿法蚀刻是使用dHF的湿法蚀刻。
在一些实施例中,在工艺(a)中预先选择的目标部分是选择性重整的目标部分,其中工艺(b)包含:(ei)使用前体和由在两个电极之间施加RF功率产生的等离子体激发的反应气体,通过ALD在衬底上的阶梯的表面上沉积初始氮化硅膜的至少一部分,所述衬底与两个电极平行地放置在所述两个电极之间,其中在ALD的每个单层沉积循环中,RF功率以每单位面积衬底0.14W/cm2至1.41W/cm2施加大于五秒,从而在进行湿法蚀刻时,使目标部分的耐化学性与非目标部分的耐化学性基本上相等;(eii)使用激发的氧化气体对初始氮化硅膜的至少一部分进行氧化,以获得中间氧化硅膜的至少一部分,而不进一步沉积膜,其中初始氮化硅膜中的Si-N键转化为Si-O键;以及(eiii)根据需要重复工艺(ei)和(eii),直到获得具有所需厚度的中间氧化硅膜;然后(eiv)湿法蚀刻中间氧化硅膜,以获得最终的介电膜,从而形成具有高保形性的最终氧化硅膜。图5是表示上述拓扑选择性膜形成工艺的流程图。
在一些实施例中,工艺(eii)中的氧化使用等离子体、UV光、热或前述两种或更多种的组合进行。
在一些实施例中,工艺(ei)中使用的RF功率为每单位面积衬底0.71W/cm2至1.41W/cm2,并且工艺(eii)中的氧化是在工艺(ei)中初始氮化硅膜的ALD的每个单层沉积循环后或初始氮化硅膜的ALD的每多个单层沉积循环后进行的等离子体氧化,其中等离子体是通过在两个电极之间施加每单位面积衬底0.07W/cm2至0.71W/cm2的RF功率而产生,所述衬底与两个电极平行地放置在所述两个电极之间。
在一些实施例中,进行工艺(eiii),其中在每次即将重复工艺(ei)之前,将衬底的阶梯的表面暴露于含氢还原气体,以用含氢还原气体处理表面。
在一些实施例中,含氢还原气体是选自由H2和NH3组成的组的至少一种气体。
在一些实施例中,在工艺(eiv)中,湿法蚀刻是使用dHF的湿法蚀刻。
在一些实施例中,蚀刻是使用dHF的湿法蚀刻,其浓度为约0.1%。
本发明将参照附图中所示的优选实施例进行详细说明。然而,本发明不旨在局限于这些实施例。
图6为示出根据本发明的一个实施例的拓扑选择性膜形成的工艺顺序的时序图,其中每一列的宽度不一定表示实际时长,每一行中的线的抬高表示开启状态,而每一行中的线的下沉表示关闭状态。通过这种技术,可以通过选择性地沉积膜的目标部分(顶部部分)形成顶厚的TS-SiO膜。
在图6中,膜的目标部分(顶部部分)的选择性沉积包含三个工艺:温育工艺、氮化(沉积)工艺和氧化工艺。在温育工艺之前,将氧化硅膜作为底层膜沉积在图案化衬底上的阶梯表面上。温育工艺包含将衬底与两个电极平行地放置在所述两个电极之间,通过在两个电极之间施加RF功率(处理3),使用氮化气体(反应剂1)产生的含氮氢等离子体对氧化硅膜的表面进行各向异性氮化,其方式是主要在阶梯的顶面和底面而不是在阶梯的侧壁上对氧化硅膜的表面进行氮化,从而在氧化硅膜的表面上引入-NH端基。在温育工艺中,在一些实施例中,反应剂1的流速在500sccm至10000sccm(优选1000sccm至5000sccm)的范围内,并且处理3在1秒至20秒(优选3秒至10秒)的范围内。
接下来,开始氮化(沉积)工艺,其包含使用前体(Precursor)和由在两个电极之间施加RF功率(处理1)产生的等离子体激发的氮化气体(反应剂1),通过PEALD在经过表面处理的氧化硅膜上沉积初始氮化硅膜的至少一部分并与之接触。温育工艺中的处理3和氮化工艺中的处理1都是通过施加RF功率进行处理。尽管在处理3和处理1中RF功率施加的条件可以相同。但是,在一些实施例中,优选地,处理3使用比处理1更强的离子能量以进行各向异性表面氮化。因此,在一些实施例中,在处理3中,使用比处理1中更高的RF功率和/或更低的压力。例如,在处理3中,在100Pa至3000Pa(优选200Pa至1000Pa)的压力下施加0.07W/cm2至1.4W/cm2(优选0.14W/cm2至0.7W/cm2)范围内的RF功率,而在处理1中,在100Pa至2000Pa(优选200Pa至1000Pa)的压力下施加0.07W/cm2至1.4W/cm2(优选0.14W/cm2至0.7W/cm2)范围内的RF功率。氮化(沉积)工艺是PEALD工艺,其中用于形成单层的一个循环可以重复N次,直到获得所需厚度的氮化物膜,其中N是10至1000(优选10至30)的整数,这取决于膜的预期用途等,以便沉积具有5nm至100nm(优选10nm至30nm)厚度的氮化物膜。在PEALD的一个循环中,前体的脉冲、反应剂1的脉冲和处理1的脉冲的持续时间在0.1秒至20秒的范围内。
此后,氧化工艺包含使用由RF功率激发的氧化气体(反应剂2)对初始氮化硅膜的至少一部分进行氧化(处理2),以获得最终氧化硅膜的至少一部分,而不进一步沉积膜,其中初始氮化硅膜中的Si-N键转化为Si-O键。例如,在处理2中,在100Pa至3000Pa(优选200Pa至1000Pa)的压力下,施加0.07W/cm2至1.4W/cm2(优选0.07W/cm2至0.7W/cm2)范围内的RF功率。在氧化工艺中,在一些实施例中,反应剂2的流速在10sccm至1000sccm(优选50sccm至500sccm)的范围内,并且处理2的持续时间在0.1秒至20秒(优选0.5秒至10秒)的范围内。
在整个工艺中,在500sccm至10000sccm(优选1000sccm至5000sccm)的范围内,连续向反应室中馈送惰性气体(Inert gas)。另外,工艺的温度可以在0℃至600℃(优选200℃至500℃)的范围内。
此外,根据需要,温育工艺、氮化工艺和氧化工艺可以重复M次,直到获得具有所需厚度的最终氧化硅膜,其中M为1至30(优选1至15)的整数,这取决于膜的预期用途等。
图9示出了示意性截面视图,其显示了根据图6中示出的时序图所表示的一个实施例的拓扑选择性膜形成工艺。状态(a)表示在状态(b)之前的状态,其中在具有阶梯42(沟槽)的衬底41的表面上形成SiO膜43。状态(b)表示温育工艺时的状态,其中SiO膜43的表面被各向异性含氮等离子体氮化,以便在SiO表面上引入-NH端基,从而在SiO膜43上形成SiNH表面44。状态(c)表示氮化工艺时的状态,其中SiN膜46通过PEALD沉积并生长在SiNH表面44上。当SiN膜46经受氧化工艺时,SiN膜46被转化为类似于状态(a)的SiN膜43的SiN膜。然后,重复这些过程,从而在衬底上获得所需的最终SiO膜(顶厚的TS-SiO膜)。
在一些实施例中,选择性沉积方案可以在下表1所示的条件下进行。
表1(数值为近似值)
图7为示出根据本发明的另一个实施例的拓扑选择性膜形成的工艺顺序的图,其中灰色的单元格表示开启状态,而白色的单元格表示关闭状态,并且每一列的宽度不代表每个工艺的持续时间。通过这种技术,可以通过选择性地去除膜的目标部分(侧壁)来形成顶厚的TS-SiO膜,并且还可以通过选择性地重整膜的目标部分(相对于侧壁的顶面)来形成保形的TS-SiO膜。
该工艺顺序包含氮化/沉积工艺(“进料”→“吹扫”→“RF脉冲-1(氮化/还原)”→“吹扫”)、氧化工艺(“反应剂-2进入”→“RF脉冲-2(氧化)”→“吹扫”)和湿法蚀刻工艺(“DHF浸渍”)。氮化工艺包含使用前体(Si前体)和由在两个电极之间施加RF功率(RF)产生的等离子体激发的反应气体(反应剂-1),通过PEALD在衬底上的阶梯表面上沉积初始氮化硅膜的至少一部分,所述衬底与两个电极平行地放置在所述两个电极之间,其中在PEALD的每个单层沉积循环中,RF功率以每单位面积衬底0.14W/cm2至1.41W/cm2(优选0.07W/cm2至0.71W/cm2)施加五秒或更短的时间(优选1秒至3秒),从而在进行湿法蚀刻时使目标部分(侧壁)的耐化学性(湿法蚀刻抗性)低于非目标部分的耐化学性。通过使用上述RF功率应用条件,与沉积在顶面/底面的膜的一部分相比,沉积在侧壁上的膜的一部分被氮化得不足以维持对湿法蚀刻的抗性,从而允许通过湿法蚀刻选择性地去除侧壁部分。
氮化(沉积)工艺是PEALD工艺,其中用于形成单层的一个循环可以重复q次,直到获得所需厚度的氮化物膜,其中q是10至1000(优选30至500)的整数,这取决于膜的预期用途等,以便沉积具有5nm至100nm(优选10nm至30nm)厚度的氮化物膜。在PEALD的一个循环中,“Si-前体”的脉冲、“反应剂-1”的脉冲和“RF”的脉冲的持续时间在0.1秒至20秒(优选0.1秒至10秒)的范围内。在一些实施例中,RF功率是在100Pa至2000Pa(优选200Pa至1000Pa)的压力下施加的。在氮化工艺中,在一些实施例中,反应剂-1的流速在500sccm至10000sccm(优选2000sccm至5000sccm)的范围内。在这个实施例中,“反应剂-1”和“运载气体/稀释气体”连续流动。
接下来,开始氧化工艺,其包含使用由RF功率(RF)激发的氧化气体(反应剂-2)对初始氮化硅膜的至少一部分进行氧化,以获得中间氧化硅膜的至少一部分,而不进一步沉积膜,其中初始氮化硅膜中的Si-N键转化为Si-O键。例如,在100Pa至2000Pa(优选200Pa至1000Pa)的压力下,施加0.07W/cm2至1.4W/cm2(优选0.07W/cm2至0.7W/cm2)范围内的RF功率。在氧化工艺中,在一些实施例中,“反应剂-2”的流速在10sccm至1000sccm(优选50sccm至500sccm)的范围内,并且“RF”的持续时间在0.1秒至10秒(优选0.1秒至5秒)的范围内。
在整个工艺中,运载气体和/或稀释气体可以在500sccm至10000sccm(优选1000sccm至5000sccm)的范围内连续馈送至反应室中。另外,工艺的温度可以在0℃至600℃(优选200℃至500℃)的范围内。
此外,根据需要,氮化/沉积工艺和氧化工艺重复p次,直到获得具有所需厚度的中间氧化硅膜,其中p是1至30(优选1至15)的整数,这取决于膜的预期用途等。
此后,开始湿法蚀刻工艺(DHF浸渍),其包含湿法蚀刻中间氧化硅膜以获得最终介电膜,从而参照非目标部分主要去除目标部分(侧壁)。在一些实施例中,湿法蚀刻可以通过使用稀释为0.1%至1.5%的氢氟酸或其已知的或新的合适的等效物/替代物在15℃至25℃的温度下蚀刻衬底30秒至600秒来进行。
图10示出了示意性截面视图,其显示了根据图7中示出的工艺顺序所代表的一个实施例的拓扑选择性膜形成工艺。状态(a)表示氮化/沉积工艺时的状态,其中在具有阶梯52(沟槽)的衬底51的表面上形成SiN膜53。状态(b)表示氧化工艺时的状态,其中SiN膜53经受氧化工艺,并且SiN膜53被转化为SiO膜54。此后,根据需要,重复氮化/沉积工艺和氧化工艺,直到获得所需厚度的SiO膜。状态(c)表示湿法蚀刻时的状态,其中通过湿法蚀刻,由于沉积在侧壁上的膜的部分比顶面/底面的部分具有较低的湿法蚀刻抗性,因此,膜的侧壁部分可以选择性地显著去除或选择性地完全去除,而其它部分可以保持显著的厚度。因此,可以在衬底上形成所需的最终SiO膜(顶厚的TS-SiO膜)。
通过使用图7所示的相同工艺,除了在两个电极之间施加的RF功率为每单位面积的衬底0.14W/cm2至1.41W/cm2(优选0.07W/cm2至0.71W/cm2),在ALD的每个单层沉积循环中持续大于五秒,所得SiO膜的膜特性如湿法蚀刻抗性可以在沉积在顶面的膜的一部分、沉积在侧壁的膜的一部分和沉积在底面的膜的一部分之间变得基本上相等,由此在湿法蚀刻之后,可以形成保形SiO膜(无碳)。
图11示出了示意性截面视图,其显示了由图7所示的工艺顺序所代表的拓扑拓扑选择性膜形成工艺,其如上文所论述进行了修改。状态(a)表示氮化/沉积工艺时的状态,其中在具有阶梯62(沟槽)的衬底61的表面上形成SiN膜63。状态(b)表示氧化工艺时的状态,其中SiN膜63经受氧化工艺,并且SiN膜63被转化为SiO膜64。此后,根据需要,重复氮化/沉积工艺和氧化工艺,直到获得所需厚度的SiO膜。状态(c)表示湿法蚀刻时的状态,其中通过湿法蚀刻,由于沉积在顶面的膜的部分、沉积在侧壁的膜的部分和沉积在底面的膜的部分对湿法蚀刻具有基本上相似的抗性,因此,所有的部分都根据需要进行基本上同等的蚀刻。因此,可以在衬底上形成所需的最终SiO膜(保形无碳、均匀的TS-SiO膜)。
在一些实施例中,可以在下表2所示的条件下进行目标部分的选择性去除(图10)和目标部分的选择性重整(图11)中的氮化。
表2(数值为近似值)
在一些实施例中,在选择性重整方案中,为了提高膜的保形性,含氮气体的流速比选择性去除方案中的流速大,并且RF功率施加时间也比选择性去除方案中的时间长。换句话说,在一些实施例中,在选择性去除方案中,为了提高膜在平坦(水平)表面上相对于在竖直表面上的生长,含氮气体的流速小于选择性重整方案中的流速,并且RF功率施加时间也比选择性重整方案中的时间短。
图8为示出膜形成的常规工艺顺序的图,其中灰色的单元格表示开启状态,而白色的单元格表示关闭状态,并且每一列的宽度不代表每个工艺的持续时间。由于在常规工艺中,没有进行与上述讨论的有关本发明实施例的工艺相对应或等同的工艺,所以从逻辑上讲,不会形成保形的无碳、均匀的SiO膜。
在本公开中描述的工艺顺序中,可使用连续供给的运载气体以脉冲形式供给前体。这可以使用流通系统(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,并且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体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体气体一起从瓶中流出。这样,运载气体可连续地流进反应室中并可通过切换主管线和绕道管线而以脉冲形式携带前体气体。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,运载气体诸如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。运载气体从瓶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。当仅将运载气体(稀有气体)馈送到反应室时,如图1B中的(b)中所示,运载气体流过具有阀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。
前体可借助于运载气体提供。由于ALD是自限性吸附反应过程,因此所沉积的前体分子的数量由反应性表面位点的数量决定,并且在饱和后与前体暴露无关,由此每一循环对前体的供应使得反应性表面位点是饱和的。用于沉积的等离子体可以原位生成,例如,在整个沉积循环中连续流动的氨气中。在其它实施例中,可远程生成等离子体并提供给反应室。
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性的。在每一阶段供应过量的反应剂以使敏感的结构表面饱和。表面饱和确保了反应剂占据所有可获得的反应位点(例如,受到物理尺寸或“位阻”限制),因此确保了优良的阶梯覆盖率。在一些实施例中,可以减少一种或多种反应剂的脉冲时间,使得不实现完全饱和并且少于一个单层吸附于衬底表面上。
工艺循环可使用任何合适的装置进行,包括例如图1A所示的装置。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工序的控制装置结合,可用于本发明的一些实施例中。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。
在一些实施例中,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。
在一些实施例中,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它方式配置为使得沉积和本文别处描述的反应器清洁工艺能够进行的控制器(未示出)。如熟练技术人员应理解,所述一个或多个控制器可与各种电源、加热系统、泵、机器人装置和反应器的气体流量控制器或阀门连通。
参考以下工作实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。
实例
实例1
在此实例中,进行如图5所示的膜的目标部分的选择性重整。首先,通过PEALD在具有沟槽(开口为30nm,纵横比为3)的Si衬底(Ф300mm)上形成厚度为20nm的SiN膜,然后,使用图1A所示的PEALD装置和图1B所示的气体供应系统(FPS),在下文表3所示的常见条件和表4所示的特定条件下,根据图7所示的工艺顺序将SiN膜转化为SiO膜。其后,在下表3所示的条件下对衬底进行湿法蚀刻。作为比较例,根据图8所示的工艺顺序,以类似于上述的方式沉积SiO膜,其中没有进行氮化/沉积工艺和氧化(转化)工艺。
表3(数值为近似值)
表4(数值为近似值)
评估每个SiO膜并且结果显示于下表5中。
表5(数值为近似值)
在表5中,“按吹扫时间的GPC趋势”中的“饱和”表示根据GPC(每循环的生长),吹扫工艺是以在吸附的前体饱和的情况下进行PEALD的每一循环的反应工艺的方式进行;“侧面覆盖率”是指保形性(%);“PLE”是指窄尺寸和宽尺寸的比率;“100:1DHF-WERR(TOX比率)”是指相对于使用稀释为1%的氢氟酸的热氧化物膜的湿法蚀刻速率;“碳”中的“<5”是指检测到的碳小于5原子%;“ND”是指“未检测到”。
如表5所示,根据实例,所有实例中获得的SiO膜均为高质量的保形无碳SiO膜,而在比较例中,SiO膜为较低质量的SiOC膜。
本领域技术人员应理解,可作多种多样的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 (20)
1.一种用于在衬底上形成的具有顶面、侧壁和底面的阶梯上形成氧化硅膜的方法,其包含以下工艺:
(a)设计最终氧化硅膜的拓扑结构,所述最终氧化硅膜是保形膜或具有低保形性的膜,通过预先选择初始氮化硅膜的目标部分,参照所述初始氮化硅膜的非目标部分,选择性地沉积或去除或重整产生所述最终氧化硅膜而在所述阶梯上形成,所述选择性沉积的目标部分是在所述阶梯的所述顶面和底面形成的所述初始氮化硅膜的顶部/底部部分,所述选择性去除或重整的目标部分是在所述阶梯的所述侧壁上形成的所述初始氮化硅膜的侧壁部分;以及
(b)根据工艺(a)中设计的拓扑结构在所述阶梯的表面上形成所述初始氮化硅膜和所述最终氧化硅膜,其中所述初始氮化硅膜使用含卤素的含硅前体通过原子层沉积(ALD)来沉积,并且所述初始氮化硅膜通过氧化所述初始氮化硅膜而转化为所述最终氧化硅膜,而不进一步沉积膜,其中所述初始氮化硅膜中的Si-N键转化为Si-O键。
2.根据权利要求1所述的方法,其中工艺(b)中使用的前体不含碳,并且所述最终氧化硅膜不含碳。
3.根据权利要求1所述的方法,其中所述初始氮化硅膜的形成和所述初始氮化硅膜的氧化在工艺(b)中在同一反应空间中连续进行。
4.根据权利要求3所述的方法,其中在所述初始氮化硅膜的形成之后,在所述初始氮化硅膜的氧化之前对所述反应空间进行吹扫,并且所述初始氮化硅膜的氧化是在引入氧化气体的所述反应空间中进行的等离子体氧化,所述氧化气体是选自由O2、O3、CO2、N2O和H2O组成的组中的至少一种气体。
5.根据权利要求1所述的方法,其中所述初始氮化硅膜由多个单层构成,并且在工艺(b)中,所述初始氮化硅膜的氧化在所述初始氮化硅膜的ALD的每个单层沉积循环之后或在所述初始氮化硅膜的ALD的每多个单层沉积循环之后进行。
6.根据权利要求1所述的方法,其中工艺(a)中预先选择的目标部分是所述选择性沉积的目标部分,其中工艺(b)包含:
(ci)在所述衬底上的所述阶梯的表面上沉积氧化硅膜;
(cii)将所述衬底与两个电极平行地放置在所述两个电极之间,以主要在所述阶梯的所述顶面和底面而不是在所述阶梯的所述侧壁上对所述氧化硅膜的表面进行氮化的方式,使用在所述两个电极之间施加RF功率产生的含氮氢等离子体对所述氧化硅膜的表面进行各向异性氮化,从而在所述氧化硅膜的表面上引入-NH端基;
(ciii)使用所述前体和由在所述两个电极之间施加RF功率产生的等离子体激发的氮化气体,通过ALD在所述经过表面处理的氧化硅膜上沉积所述初始氮化硅膜的至少一部分并与所述经过表面处理的氧化硅膜接触;
(civ)使用激发的氧化气体对所述初始氮化硅膜的所述至少一部分进行氧化,以获得所述最终氧化硅膜的至少一部分,而不进一步沉积膜,其中所述初始氮化硅膜中的Si-N键转化为Si-O键;以及
(cv)根据需要,重复工艺(cii)和(civ),直到获得具有所需厚度的所述最终氧化硅膜。
7.根据权利要求6所述的方法,其中工艺(cii)中的所述含氮氢等离子体使用N2和H2的混合物、NH3、其它NxHy生成,其中x和y为整数,或使用前述两种或更多种的混合物生成。
8.根据权利要求6所述的方法,其中工艺(ci)中的所述氧化硅膜通过ALD或CVD沉积。
9.根据权利要求1所述的方法,其中工艺(a)中预先选择的所述目标部分是所述选择性去除的目标部分,其中工艺(b)包含:
(di)使用所述前体和由在两个电极之间施加RF功率产生的等离子体激发的反应气体,通过ALD在所述衬底上的所述阶梯的表面上沉积所述初始氮化硅膜的至少一部分,所述衬底与两个电极平行地放置在所述两个电极之间,其中在ALD的每个单层沉积循环中,RF功率以每单位面积所述衬底0.14W/cm2至1.41W/cm2施加五秒或更短的时间,从而使所述目标部分比所述非目标部分在进行湿法蚀刻时具有更低的耐化学性;
(dii)使用激发的氧化气体对所述初始氮化硅膜的所述至少一部分进行氧化,以获得中间氧化硅膜的至少一部分,而不进一步沉积膜,其中所述初始氮化硅膜中的Si-N键转化为Si-O键;以及
(diii)根据需要,重复工艺(di)和(dii),直到获得具有所需厚度的所述中间氧化硅膜;然后
(div)湿法蚀刻所述中间氧化硅膜,以获得最终的介电膜,从而参照所述非目标部分主要去除所述目标部分。
10.根据权利要求9所述的方法,其中工艺(dii)中的氧化使用等离子体、UV光、热或前述两种或更多种的组合进行。
11.根据权利要求9所述的方法,其中工艺(di)中使用的RF功率为每单位面积所述衬底0.14W/cm2至0.71W/cm2,并且工艺(dii)中的氧化是在工艺(di)中所述初始氮化硅膜的ALD的每个单层沉积循环后或所述初始氮化硅膜的ALD的每多个单层沉积循环后进行的等离子体氧化,其中所述等离子体是通过在两个电极之间施加每单位面积所述衬底0.07W/cm2至0.71W/cm2的RF功率而产生,所述衬底与两个电极平行地放置在所述两个电极之间。
12.根据权利要求9所述的方法,其中进行工艺(diii),其中在每次即将重复工艺(di)之前,将所述衬底的所述阶梯的表面暴露于含氢还原气体,以用所述含氢还原气体处理所述表面。
13.根据权利要求12所述的方法,其中所述含氢还原气体是选自由H2和NH3组成的组的至少一种气体。
14.根据权利要求9所述的方法,其中在工艺(div)中,所述湿法蚀刻是使用dHF的湿法蚀刻。
15.根据权利要求1所述的方法,其中工艺(a)中预先选择的所述目标部分是选择性重整的目标部分,其中工艺(b)包含:
(ei)使用所述前体和由在两个电极之间施加RF功率产生的等离子体激发的反应气体,通过ALD在所述衬底上的所述阶梯的表面上沉积所述初始氮化硅膜的至少一部分,所述衬底与两个电极平行地放置在所述两个电极之间,其中在ALD的每个单层沉积循环中,RF功率以每单位面积所述衬底0.14W/cm2至1.41W/cm2施加大于五秒,从而在进行湿法蚀刻时,使所述目标部分的耐化学性与所述非目标部分的耐化学性基本上相等;
(eii)使用激发的氧化气体对所述初始氮化硅膜的所述至少一部分进行氧化,以获得中间氧化硅膜的至少一部分,而不进一步沉积膜,其中所述初始氮化硅膜中的Si-N键转化为Si-O键;以及
(eiii)根据需要重复工艺(ei)和(eii),直到获得具有所需厚度的所述中间氧化硅膜,其中如果未进行可选的工艺(eiv),则将所述中间氧化硅膜视为具有高保形性的所述最终氧化硅膜;然后
(eiv)任选地湿法蚀刻所述中间氧化硅膜以调整所述中间氧化硅膜的保形性,以获得最终的介电膜,从而形成具有高保形性的所述最终氧化硅膜。
16.根据权利要求15所述的方法,其中工艺(eii)中的氧化使用等离子体、UV光、热或前述两种或更多种的组合进行。
17.根据权利要求15所述的方法,其中工艺(ei)中使用的RF功率为每单位面积所述衬底0.71W/cm2至1.41W/cm2,并且工艺(eii)中的氧化是在工艺(ei)中所述初始氮化硅膜的ALD的每个单层沉积循环后或所述初始氮化硅膜的ALD的每多个单层沉积循环后进行的等离子体氧化,其中所述等离子体是通过在两个电极之间施加每单位面积所述衬底0.07W/cm2至0.71W/cm2的RF功率而产生,所述衬底与两个电极平行地放置在所述两个电极之间。
18.根据权利要求15所述的方法,其中进行工艺(eiii),其中在每次即将重复工艺(ei)之前,将所述衬底的所述阶梯的表面暴露于含氢还原气体,以用所述含氢还原气体处理所述表面。
19.根据权利要求18所述的方法,其中所述含氢还原气体是选自由H2和NH3组成的组的至少一种气体。
20.根据权利要求15所述的方法,其中在工艺(eiv)中,所述湿法蚀刻是使用dHF的湿法蚀刻。
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CN113394067A (zh) | 2020-03-13 | 2021-09-14 | Asm Ip私人控股有限公司 | 基板处理设备 |
US20210292902A1 (en) | 2020-03-17 | 2021-09-23 | Asm Ip Holding B.V. | Method of depositing epitaxial material, structure formed using the method, and system for performing the method |
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US11821078B2 (en) | 2020-04-15 | 2023-11-21 | Asm Ip Holding B.V. | Method for forming precoat film and method for forming silicon-containing film |
KR20210128343A (ko) | 2020-04-15 | 2021-10-26 | 에이에스엠 아이피 홀딩 비.브이. | 크롬 나이트라이드 층을 형성하는 방법 및 크롬 나이트라이드 층을 포함하는 구조 |
US11996289B2 (en) | 2020-04-16 | 2024-05-28 | Asm Ip Holding B.V. | Methods of forming structures including silicon germanium and silicon layers, devices formed using the methods, and systems for performing the methods |
TW202140846A (zh) | 2020-04-17 | 2021-11-01 | 荷蘭商Asm Ip私人控股有限公司 | 注入器、及垂直熔爐 |
TW202143328A (zh) | 2020-04-21 | 2021-11-16 | 荷蘭商Asm Ip私人控股有限公司 | 用於調整膜應力之方法 |
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2020
- 2020-10-07 TW TW109134744A patent/TWI834919B/zh active
- 2020-10-08 KR KR1020200129895A patent/KR20210045930A/ko unknown
- 2020-10-12 US US17/068,495 patent/US11637011B2/en active Active
- 2020-10-12 CN CN202011082907.9A patent/CN112670156A/zh active Pending
- 2020-10-12 JP JP2020171798A patent/JP2021064788A/ja active Pending
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TW202129053A (zh) | 2021-08-01 |
KR20210045930A (ko) | 2021-04-27 |
TWI834919B (zh) | 2024-03-11 |
US11637011B2 (en) | 2023-04-25 |
US20210118667A1 (en) | 2021-04-22 |
JP2021064788A (ja) | 2021-04-22 |
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