CN111524788A - 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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- CN111524788A CN111524788A CN202010057814.4A CN202010057814A CN111524788A CN 111524788 A CN111524788 A CN 111524788A CN 202010057814 A CN202010057814 A CN 202010057814A CN 111524788 A CN111524788 A CN 111524788A
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- film
- dielectric film
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- impurities
- initial dielectric
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- 238000000034 method Methods 0.000 title claims abstract description 68
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title description 21
- 230000015572 biosynthetic process Effects 0.000 title description 16
- 229910052814 silicon oxide Inorganic materials 0.000 title description 11
- 239000012535 impurity Substances 0.000 claims abstract description 120
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000758 substrate Substances 0.000 claims abstract description 47
- 238000000151 deposition Methods 0.000 claims abstract description 45
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000005530 etching Methods 0.000 claims abstract description 13
- 229910018557 Si O Inorganic materials 0.000 claims abstract description 11
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- 238000001039 wet etching Methods 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 21
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910007245 Si2Cl6 Inorganic materials 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N carbon tetrachloride Substances ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
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- 125000001424 substituent group Chemical group 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
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Abstract
一种用于在衬底的上表面中形成的沟槽中形成含有Si‑O键的介电膜的方法,其包括:通过相对于初始介电膜的非目标部分预先选择待选择性去除的目标部分来设计形成在沟槽中的含有Si‑O键的最终介电膜的拓扑,从而产生最终介电膜;在上表面上和沟槽中保形地沉积初始介电膜;以及相对于初始介电膜的非目标部分中所含的杂质的量相对增加初始介电膜的目标部分中所含的杂质的量以获得经处理的介电膜,从而赋予目标部分和非目标部分在经受蚀刻时不同的耐化学性。
Description
技术领域
本发明总的涉及一种用于在衬底的表面上形成的阶梯上形成含有Si-O键的介电膜的方法,特别是涉及一种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)的特征不仅在于对膜厚度的优异控制性和膜的优异均匀性,而且在于能够沉积均匀覆盖三维结构的膜,并因此,ALD已被认为是半导体工业中一种非常重要的沉积方法。在另一个方面,在某些半导体器件制造过程中,需要不均匀地形成膜,例如在栅极间隔件中,其中仅沉积在沟槽中的膜的侧壁部分选择性地留在某些区域中,并且在此情况下,通过ALD的膜沉积与各向异性干法蚀刻结合使用以形成期望的图案。然而,由于难以确定干法蚀刻的终点,故存在过度蚀刻的问题,此时下面的层会受损。
作为这种图案化技术,已知首先在一定的条件下于衬底的图案化表面上沉积SiN膜使得图案的水平部分和竖直部分的湿法蚀刻速率不同,然后是湿法蚀刻,从而选择性地仅留下图案的侧壁部分或图案的水平部分(如例如美国专利申请公开号2017/0243734中所公开,其公开内容全文以引用方式并入本文,这适用于本文公开的某些实施方案)。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,故可以相对于下面的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
在一些实施方案中,通过借助等离子体增强ALD(PEALD)向以图案沉积在衬底上的SiO2膜引入杂质,可操纵HF(氢氟酸)对膜的湿法蚀刻速率,从而选择性地基本上仅或主要地留下衬底上形成的图案的竖直或水平部分。在一些实施方案中,使用卤素原子和/或碳原子作为杂质。在一些实施方案中,通过以拓扑方式操纵存在于衬底的图案化表面中的杂质的浓度,可调节杂质的分布,使得杂质选择性地留在图案的竖直部分中或杂质选择性地各向异性地引入图案的水平部分中,从而实现拓扑选择性膜形成。在一些实施方案中,SiO2膜中所含的杂质可源自或衍生自前体和/或可后续通过使用非硅气体进行的附加膜形成或附加表面处理引入到SiO2膜的表面。在一些实施方案中,杂质的后续引入通过PECVD或PEALD实现,其中后续引入循环在每一个沉积循环或多个沉积循环之后进行。
特别地,举例来说,TS-SiO可如下进行:
1)首先,使用含有碳和/或卤素的前体沉积SiO2膜;然后,将SiO2膜暴露于在较低压力和较高RF功率下生成的等离子体,从而在SiO2膜中形成杂质的各向异性分布,其中与从图案的竖直部分相比,SiO2膜中所含的杂质被显著更多地从图案的水平部分选择性去除。在每一个沉积循环或多个沉积循环之后进行杂质去除循环。
2)首先,沉积SiO2膜;其次,通过将SiO2膜的表面暴露于含有碳和/或卤素作为杂质的非硅气体以向SiO2膜的表面吸附杂质;然后,将吸附了杂质的SiO2膜暴露于在较低压力和较高RF功率下生成的等离子体,从而在SiO2膜中形成杂质的各向异性分布,其中与到图案的水平部分相比,杂质被显著更多地选择性引入到图案的竖直部分。在每一个沉积循环或多个沉积循环之后进行杂质添加循环。在上文中,为了沉积SiO2膜,可使用任何合适的含硅前体,而不管该前体是否含有碳和/或卤素。
3)在上面的步骤1)或2)之后,使用dHF使SiO2膜经受湿法蚀刻,从而选择性地去除比图案的剩余部分含有更多杂质的图案的一部分,由此可实现TS-SiO,其中可基本上仅或主要地选择性去除图案的竖直或水平部分。
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为可用于本发明的一个实施方案中的用来沉积保护膜的PEALD(等离子体增强原子层沉积)装置的示意图。
图1B示意了可用于本发明的一个实施方案中的使用流通系统(FPS)的前体供给系统的示意图。
图2为流程图,示意了根据本发明的一个实施方案的拓扑选择性膜形成的步骤。
图3为流程图,示意了根据本发明的另一个实施方案的拓扑选择性膜形成的步骤。
图4为流程图,示意了根据本发明的还另一个实施方案的拓扑选择性膜形成的步骤。
图5示意了示意性横截面视图,其示出了根据本发明的不同实施方案的拓扑选择性膜形成的过程((a)和(b)表示一个实施方案,而(a)和(c)表示另一个实施方案)。
图6示出了(a)沉积状态的氧化硅膜、(b)无改造处理情况下经dHF蚀刻后的氧化硅膜、和(c)根据本发明的一个实施方案的改造处理后经dHF蚀刻后的氧化硅膜的横截面视图的扫描电子显微镜(SEM)照片。
图7为曲线图,示出了根据本发明的实施方案在顶表面上形成的膜(覆盖膜)的处理压力[kPa]与湿法蚀刻速率(“WERR.Tox”:相对于热氧化物的湿法蚀刻速率)之间的关系。
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。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。
在本公开中,“退火”是指将材料处理成其稳定形式的过程,例如,将组分中存在的末端基团(如醇基团和羟基基团)替换为更稳定的基团(如Si-Me基团)和/或形成更稳定的形式(如Si-O键),这通常引起膜的致密化。
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,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。
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。
一些实施方案提供了一种用于在衬底的表面上形成的阶梯上形成含有Si-O键的介电膜的方法,其包括过程:(i)通过参照初始介电膜的非目标部分预先选择待选择性去除的目标部分来设计形成在阶梯上的含有Si-O键的最终介电膜的拓扑,从而产生最终介电膜,所述目标部分为形成在阶梯的顶表面和底表面上的初始介电膜的顶部/底部部分或形成在阶梯的侧壁上的初始介电膜的侧壁部分;(ii)在阶梯的顶表面、底表面和侧壁上保形地沉积初始介电膜;(iii)相对于初始介电膜的非目标部分中所含的杂质的量相对增加初始介电膜的目标部分中所含的杂质的量以获得经处理的介电膜,从而赋予目标部分和非目标部分在经受蚀刻时不同的耐化学性;和(iv)蚀刻所述经处理的介电膜以获得最终介电膜。因此,可基本上仅或主要地去除图案的竖直或水平部分,从而实现SiO的拓扑选择性膜形成。在本公开中,术语“基本上”等可指本领域技术人员认为对于预期目的或功能将足够的充足、相当大或实质性的量、尺寸、时间或空间(例如,相对于相关部分的总值或参考值的至少70%、80%、90%、或95%)。例如,术语“基本上仅”等可指其中目标部分与剩余部分在厚度上的比率为至少70/30、80/20、90/10或95/5的配置。
在本公开中,术语“阶梯”是指衬底中形成的任何凹形和/或凸形图案,包括但不限于沟槽,并且在一些实施方案中,沟槽可具有约10至约50nm(通常约15至约30nm)的宽度(其中当沟槽具有与宽度基本上相同的长度时,其被称为孔/通孔,且其直径为约10至约50nm)、约30至约200nm(通常约50至约150nm)的深度和约3至约20(通常约3至约10)的纵横比。在一些实施方案中,沉积在衬底的上表面上和沟槽中的氧化硅膜具有约70%至约100%(通常约80%或更高、更通常约90%或更高)的保形性,其中“保形性”通过比较在侧壁上或凹槽底部上的某些点(通常为横截面视图中的中点)处沉积的膜厚度与在恰好凹槽外的平坦表面上沉积的膜厚度来确定。
在一些实施方案中,杂质包括碳和/或卤素。
在一些实施方案中,在过程(i)中,预先选择侧壁部分为目标部分,在过程(ii)中,使用还含有碳和/或卤素的含硅前体沉积初始介电膜,在过程(iii)中,通过减少初始介电膜的非目标部分中所含的杂质的量来相对增加目标部分中所含的杂质的量,所述减少通过由在两个电极之间施加RF功率所激发的等离子体的各向异性轰击来实现,衬底与两个电极平行地放置在两个电极之间。本实施方案可被称为“通过杂质的区域选择性去除实现的顶部/底部厚TS-SiO”。在此实施方案中,通过由等离子体各向异性离子轰击,主要是膜的水平部分被附着,并因此,相对于膜的竖直部分,水平部分变得致密化并且杂质从水平部分选择性地离解或分离并去除,从而区域选择性地增加水平部分中的耐化学性并降低其湿法蚀刻速率(即,基本上仅或主要地留下膜的顶部/底部部分)。
在一些实施方案中,在通过杂质的区域选择性去除实现的顶部/底部厚TS-SiO中,含硅前体选自Si2RyCl6-y(其中y为0至5的整数)和SiRxCl4-x(其中R为H或烷基基团,x为0至3的整数)。例如,此类前体包括但不限于Si2Cl6、SiCl4和/或Si2Cl2(CH3)4。此外,在一些实施方案中,如针对300-mm晶片所计算,RF功率为600W至1,000W,并在1至100Pa的压力下施加。
在一些实施方案中,在过程(i)中,预先选择顶部/底部部分为目标部分,并在过程(iii)中,通过增加初始介电膜的目标部分中所含的杂质的量来相对增加目标部分中所含的杂质的量,所述增加通过(iiia)在初始介电膜的整个暴露表面上吸附含有碳和/或卤素的非硅气体和(iiib)使吸附了非硅气体的表面经受通过在两个电极之间施加RF功率所激发的等离子体的各向异性轰击来实现,衬底与两个电极平行地放置在两个电极之间。本实施方案可被称为“通过杂质的区域选择性掺入实现的侧壁厚TS-SiO”。在此实施方案中,通过向膜的表面引入杂质、然后由等离子体各向异性离子轰击,主要是膜的水平部分被附着,并因此,相对于膜的竖直部分,水平部分变得致密化并且杂质选择性地掺入和引入到水平部分,从而区域选择性地降低水平部分中的耐化学性并增加其湿法蚀刻速率(即,基本上仅或主要地留下膜的侧壁部分)。
在一些实施方案中,在过程(i)中,预先选择顶部/底部部分为目标部分,并在过程(iii)中,通过增加初始介电膜的目标部分中所含的杂质的量来相对增加目标部分中所含的杂质的量,所述增加通过(iiic)使初始介电膜经受通过在含有碳和/或卤素的非硅气体的存在下在两个电极之间施加RF功率所激发的等离子体的各向异性轰击来实现,衬底与两个电极平行地放置在两个电极之间。上述也是通过杂质的区域选择性掺入实现的侧壁厚TS-SiO。在上文中,代替过程(iiia)和(iiib),进行过程(iiic),其中杂质被包含在等离子体气体中,而不是将杂质吸附到膜的表面上,然后进行等离子体暴露。
在一些实施方案中,由于在通过杂质的区域选择性掺入实现的侧壁厚TS-SiO中使用非硅气体来向膜中引入杂质,故前体本身不含杂质并可以是通常使用的那些。例如,这样的前体包括但不限于NxHy(x和y为非零整数)、NxCyHz(x、y和z为非零整数)和/或N2。在一些实施方案中,前体不含碳或卤素。
在一些实施方案中,在通过杂质的区域选择性掺入实现的侧壁厚TS-SiO中,非硅气体选自烃类气体、卤素气体和卤化气体。例如,这样的非硅气体包括但不限于CH4、C2H6、Cl2、Br2、CCl4等,或其他烃、卤素和卤化气体,其通常为液体并且具有10托或更高的蒸气压。此外,在一些实施方案中,如针对300-mm晶片所计算,RF功率为600W至1,000W,并在1至100Pa的压力下施加。
在一些实施方案中,在过程(ii)中,通过等离子体增强ALD或热ALD沉积初始介电膜。
在一些实施方案中,在过程(iv)中,蚀刻为使用dHF的湿法蚀刻。在一些实施方案中,HF的浓度为大约0.1%。
本发明将参照附图中所示的优选实施方案进行详细说明。然而,本发明不旨在局限于这代表些实施方案。
图2为流程图,示意了根据本发明的实施方案的SiO(TS-SiO)的拓扑选择性膜形成的过程,其为通过杂质的区域选择性去除实现的顶部/底部厚TS-SiO。在步骤S1中,使用含有杂质的前体在具有沟槽的衬底上沉积SiO膜。沉积可通过任何合适的方法进行,如PEALD、热ALD、循环CVD或PECVD。在步骤S2中,将沉积膜在较低压力和较高RF功率下暴露于惰性气体等离子体,使得与膜的竖直部分中所含的杂质相比,膜的水平部分中所含的杂质被主要或充分去除。步骤S1和步骤S2无中断地连续进行(不破坏真空),使得没有或几乎没有杂质在步骤S1和步骤S2之间从衬底周围的大气中掺入或吸附到沉积膜的表面上。当步骤S1为循环沉积时,步骤S2可在循环沉积的每一个循环(沉积单层)之后进行或在循环沉积的每两个或更多个循环(沉积单层的层合物)之后进行。然而,步骤S1中获得的膜的厚度应不超过步骤S2中等离子体的离子轰击将无法穿透的厚度。一组步骤S1和步骤S2可重复多次,直至获得所需的膜厚度。在一些实施方案中,取决于沉积膜的预期目的或用途,顶表面上沉积膜的厚度为约3nm至约50nm,通常约10nm至约30nm。在一些实施方案中,步骤S2可在下表1中所示的条件下进行。
表1(数值为近似值)
可将“W”转换为衬底每单位面积的“W/cm2”,并可将单位为W/cm2的转换值应用于不同尺寸的衬底如200-mm衬底和450-mm衬底。由于处理的效果取决于等离子体的离子能量,故对于沉积后处理,施加到反应空间的合适RF功率根据反应空间的压力确定。因此,举例来说,通常,压力为约400Pa或更小(优选约100Pa或更小),并且RF功率为约600W或更高(例如,在400Pa下),其中压力越低,可施加越低的RF功率。由于SiO2膜的沉积可使用常用的RF功率进行,故当沉积后处理开始时,通常增加RF功率。在沉积后处理中,通常,当施加增加的RF功率时,膜的水平部分的耐化学性将变高,例如降低湿法蚀刻速率,因为可从膜的水平部分去除更多杂质。然而,如果RF功率变得太高,则膜的水平部分将受损并且其耐化学性将变低,例如增加湿法蚀刻速率。即,RF功率(由水平轴线表示)与耐化学性(由竖直轴线表示)之间的关系可由具有最小值的向下曲线表示,所述最小值指示最佳RF功率。相应地,鉴于本公开,可针对预先选择的压力(最佳RF功率根据压力变化)通过常规实验确定最佳RF功率。
在一些实施方案中,在步骤S2中,没有非惰性气体的气体被引入到反应空间。在一些实施方案中,在步骤S2中可另外地或替代地以相似的流率引入氢气。在一些实施方案中,在步骤S2中,没有引入氧气、氮气或其他反应物或前体气体。
在步骤S3中,使经等离子体处理的膜经受湿法蚀刻以实现TS-SiO。通过步骤S2,杂质从膜的水平部分(即,膜的顶部/底部部分)区域选择性地去除,并且膜的水平部分变得致密化并增加耐化学性。通过使经等离子体处理的膜经受湿法蚀刻,主要是比膜的水平部分含有更多杂质的膜的竖直部分(即,膜的侧壁部分)被蚀刻或去除,从而形成顶部/底部厚轮廓。在一些实施方案中,步骤S3可在下表2中所示的条件下进行。
表2(数值为近似值)
对于湿法蚀刻,可使用任何合适的单晶片式或分批式装置,包括任何常规装置。另外,可使用任何适用于湿法蚀刻的溶液,包括任何常规溶液。由于膜的主要组分由SiO2构成,故如果使用高浓度HF溶液进行湿法蚀刻,则湿法蚀刻选择性将不够。因此,通常使用低浓度HF溶液如约0.1%溶液进行湿法蚀刻。
图3为流程图,示意了根据本发明的另一个实施方案的拓扑选择性膜形成的过程。本实施方案代表通过杂质的区域选择性掺入实现的侧壁厚TS-SiO。在步骤S4中,在具有沟槽的衬底上沉积SiO膜。沉积可通过任何合适的方法进行,如PEALD、热ALD、循环CVD或PECVD。在步骤S5中,在等离子体暴露之前使杂质吸附到膜的表面上。步骤S5可通过将膜暴露于含有杂质如碳和/或卤素但不含硅的烃类气体或类似物来实现,从而将非硅气体吸附到膜的表面上。在一些实施方案中,步骤S5可在下表3中所示的条件下进行。
表3(数值为近似值)
在此实施方案中,在步骤S5之后进行等离子体处理,其中膜的表面上存在非SiO的杂质。等离子体处理可在表1中所示的条件下以与图2(代表通过杂质的区域选择性去除实现的顶部/底部厚TS-SiO)中的步骤S2基本相似的方式进行。然而,在通过杂质的区域选择性掺入实现的侧壁厚TS-SiO中,尽管事实是步骤S2可以与通过杂质的区域选择性去除实现的顶部/底部厚TS-SiO中的步骤S2基本相似的方式进行,但步骤S2的功能与通过杂质的区域选择性去除实现的顶部/底部厚TS-SiO中的步骤S2的功能完全相反。即,在通过杂质的区域选择性去除实现的顶部/底部厚TS-SiO(图2)的步骤S2中,是杂质主要从膜的水平部分被去除,而在通过杂质的区域选择性掺入实现的侧壁厚TS-SiO(图3)的步骤S2中,是杂质主要被引入到膜的水平部分中。
在步骤S2中,将吸附了杂质的膜在较低压力和较高RF功率下暴露于惰性气体等离子体,使得与吸附在膜的竖直部分上的杂质相比,吸附在膜的水平部分上的杂质被主要或充分掺入到其中。步骤S4、步骤S5和步骤S2无中断地连续进行(不破坏真空),或者,可在与用于步骤S4的腔室不同的腔室中或通过将衬底存放于含有杂质的不同气氛中进行步骤S5,并然后将衬底重新装载到用于步骤S4的腔室以进行步骤S3,如图3中所示意。当步骤S4为循环沉积时,步骤S5和S2可在循环沉积的每一个循环(沉积单层)之后进行或在循环沉积的每两个或更多个循环(沉积单层的层合物)之后进行。然而,步骤S4中获得的膜的厚度应不超过步骤S2中等离子体的离子轰击将无法穿透的厚度。一组步骤S4、S5和S2可重复多次,直至获得所需的膜厚度。在一些实施方案中,取决于沉积膜的预期目的或用途,顶表面上沉积膜的厚度为约3nm至约50nm,通常约10nm至约20nm。
在步骤S3中,在表2中所示的条件下以与图2中所示步骤S3基本相似的方式使经等离子体处理的膜经受湿法蚀刻以实现TS-SiO。通过步骤S2,杂质被区域选择性地掺入到膜的水平部分(即,膜的顶部/底部部分)中,并且膜的水平部分变得更容易受到离子轰击并降低耐化学性。通过使经等离子体处理的膜经受湿法蚀刻,主要是比膜的竖直部分含有更多杂质的膜的水平部分(即,膜的顶部/底部部分)被蚀刻或去除,从而形成侧壁厚轮廓。
图4为流程图,示意了根据本发明的另一个实施方案的拓扑选择性膜形成的过程。本实施方案代表通过杂质的区域选择性掺入实现的侧壁厚TS-SiO的另一个实施方案。在步骤S4中,以与图3的步骤S4基本相似的方式在具有沟槽的衬底上沉积SiO膜。在步骤S6中,向等离子体气体中加入含有杂质的气体(例如,含有杂质如碳和/或卤素但不含硅的烃类气体等),使得膜暴露于含有将主要掺入到膜的水平部分中作为杂质的元素的活性物种的等离子体,从而产生杂质分布类似于如图3中所示获得的膜的杂质分布的膜。在一些实施方案中,步骤S6可在下表4中所示的条件下进行。
表4(数值为近似值)
步骤S4和步骤S6无中断地连续进行(不破坏真空)。当步骤S4为循环沉积时,步骤S6可在循环沉积的每一个循环(沉积单层)之后进行或在循环沉积的每两个或更多个循环(沉积单层的层合物)之后进行。一组步骤S4和S6可重复多次,直至获得所需的膜厚度。在一些实施方案中,取决于沉积膜的预期目的或用途,顶表面上沉积膜的厚度为约3nm至约50nm,通常约10nm至约20nm。
在步骤S3中,在表3中所示的条件下以与图2中所示步骤S3基本相似的方式使经等离子体处理的膜经受湿法蚀刻以实现TS-SiO。如在图3中所示意的过程中,通过步骤S6,杂质被区域选择性地掺入到膜的水平部分(即,膜的顶部/底部部分)中,并且膜的水平部分变得更容易受到离子轰击并降低耐化学性。通过使经等离子体处理的膜经受湿法蚀刻,主要是比膜的竖直部分含有更多杂质的膜的水平部分(即,膜的顶部/底部部分)被蚀刻或去除,从而形成侧壁厚轮廓。
图5示意了示意性横截面视图,其示出了根据本发明的不同实施方案的SiO(TS-SiO)的拓扑选择性膜形成的过程((a)和(b)代表通过杂质的区域选择性去除实现的顶部/底部厚TS-SiO,而(a)和(c)代表通过杂质的区域选择性掺入实现的侧壁厚TS-SiO)。在图5中,SiO2膜42保形地沉积在具有沟槽46的衬底41上,其中SiO2膜42由水平部分(顶部部分45和底部部分43)和竖直部分(侧壁部分44)构成,所述膜保形地或均匀地覆盖具有沟槽46的衬底41的整个表面。SiO2膜42具有基本上地理上均匀的杂质分布,包括在整个膜中基本没有分布的杂质。
在通过杂质的区域选择性去除实现的顶部/底部厚TS-SiO中,(a)中的SiO2膜42含有基本上均匀分布在整个膜中的杂质,并通过将膜暴露于各向异性等离子体撞击(通过离子轰击),膜45、43的水平部分比膜44的竖直部分接收更多的离子轰击,从而与从竖直部分相比更多地从水平部分解离或分离杂质并使水平部分致密化。因此,膜的竖直部分中比膜的水平部分中保留更多的杂质,即,竖直部分变得比水平部分更容易受到湿法蚀刻。因此,通过使具有杂质的不均匀分布的膜经受湿法蚀刻,基本上仅或主要地膜的竖直部分可被去除,如(b)中所示意。
相比之下,在通过杂质的区域选择性掺入实现的侧壁厚TS-SiO中,(a)中的SiO2膜42含有基本上均匀地分布在整个膜中的杂质,包括整个膜中基本上为零或低含量的杂质,并且通过向膜的竖直和水平部分的表面上吸附杂质,然后进行等离子体暴露,或通过将膜的竖直和水平部分暴露于含有杂质的活性物种的等离子体,其中膜45、43的水平部分比膜44的竖直部分接收更多的离子轰击,从而与向竖直部分中相比将杂质更多地掺入到水平部分中。因此,膜的水平部分中比膜的竖直部分中引入了更多的杂质,即,水平部分变得比竖直部分更容易受到湿法蚀刻。因此,通过使具有杂质的不均匀分布的膜经受湿法蚀刻,基本上仅或主要地膜的水平部分可被去除,如(c)中所示意。
在一些实施方案中,在图5中(b)中示意的通过杂质的区域选择性去除实现的顶部/底部厚TS-SiO中,最终膜的保形性(侧壁处(例如,在横截面视图中的中点处)的膜厚度与顶部部分处(例如,横截面视图中的中点处)的膜厚度的比率)为约30%或更小,包括基本上0%(例如,约0%、约10%、约20%、约30%、或任何两个前述数字之间的范围中的任何数字)。在一些实施方案中,在图5中(c)中示意的通过杂质的区域选择性掺入实现的侧壁厚TS-SiO中,最终膜的保形性的倒数(侧壁处(例如,在横截面视图中的中点处)的膜厚度与膜的顶部处(例如,横截面视图中的中点处)的膜厚度的比率)为约30%或更小,包括基本上0%(例如,约0%、约10%、约20%、约30%、或任何两个前述数字之间的范围中的任何数字)。在上文中,底部处的膜厚度可随沟槽的纵横比、RF功率、压力等而异。例如,如果沟槽的纵横比高,例如为5比10或更高,RF功率较低,和/或压力较高,则与顶部处的膜相比,湿法刻蚀后沟槽的底部处的膜将倾向于保留,因为可能没有足够的等离子体离子轰击能够到达沟槽的底部。
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。
前体可借助于载气提供。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。在其他实施方案中,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物以使敏感的结构表面饱和。表面饱和确保了反应物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。在一些实施方案中,可以减少一种或多种反应物的脉冲时间,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中示意的装置。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,使得所有过程都可连续地进行而不将衬底暴露于空气或其他含氧气氛中。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)。如所属领域的技术人员应了解,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
实施例1
在此实施例中,如图4中所示进行通过杂质的区域选择性掺入实现的侧壁厚TS-SiO。然而,本实施例只是实验实施例,因为图4中的步骤S6使用聚酰亚胺胶带(具有丙烯酸类粘合剂)将衬底粘附到感受器来进行,该胶带暴露于等离子体并预期是包括碳的杂质的来源(气载分子污染物,AMC),碳被释放到等离子体中,形成含有碳的活性物种的等离子体(与通过向等离子体气体中加入含有杂质的气体来形成含有杂质的活性物种的等离子体相反)。上述步骤被认为在功能上等同于步骤S6,其中两个步骤均产生含有杂质的活性物种的等离子体。
首先,通过PEALD在具有沟槽的Si衬底(Ф300mm)上形成SiO膜,使用图1A中所示意的PEALD装置和图1B中所示意的气体供给系统(FPS)在下表5(沉积循环)中示出的条件下进行其的一个循环。
在从反应室取出衬底后,将衬底暂时存放在大气中,然后使用具有丙烯酸类粘合剂的聚酰亚胺胶带将衬底粘附到装置的感受器表面。然后在下表5中所示的条件下使衬底经受沉积后等离子体处理,使得丙烯酸类粘合剂暴露于等离子体,从而在等离子体中生成碳的活性物种。其后,在下表5中所示的条件下使衬底经受湿法蚀刻。
表5(数值为近似值)
同样,作为对比实施例,通过PEALD以与上文所述基本上相似的方式在具有沟槽的Si衬底(Ф300mm)上形成SiO膜,而不进行等离子体处理(不进行步骤S6),连续地,以与上文所述基本上相似的方式使衬底经受湿法蚀刻。
结果在图6中示出。图6示出了(a)沉积状态的氧化硅膜、(b)无等离子体处理情况下经dHF蚀刻后的氧化硅膜、和(c)等离子体处理后经dHF蚀刻后的氧化硅膜的横截面视图的扫描电子显微镜(SEM)照片。如图6中的(c)中所示,当衬底暴露于含有杂质的活性物种的等离子体时,基本上仅或主要地膜的顶部部分被蚀刻,从而基本上仅或主要地留下膜的侧壁部分。如图6中的(c)中所示,当衬底暴露于含有杂质的活性物种的等离子体时,基本上仅或主要地膜的侧壁部分被蚀刻,从而基本上仅或主要地留下膜的顶部部分。这似乎是因为等离子体中所含的杂质被基本上仅或主要地掺入到膜的顶部部分中,使得膜的顶部部分比膜的侧壁部分更容易受到湿法蚀刻。
在图6中的(b)中,在没有杂质的区域选择性去除过程的情况下实现了顶部/底部厚TS-SiO。这似乎是因为PEALD具有各向异性特性并活化了膜的水平部分而非竖直部分,从而赋予水平部分高质量(高密度和/或低杂质浓度),具体取决于沉积条件等。通过采用图2中所示意的过程,可进一步改善膜的水平部分的质量,并可进一步改善水平和竖直部分之间膜的湿法蚀刻选择性。此外,在通过热ALD沉积膜的情况下,膜质量是均匀的且原则上在膜的水平部分和竖直部分之间不存在差异。在此情况下,需要等离子体处理来实现顶部/底部厚TS-SiO。
在图6中的(c)中,膜的底部部分被蚀刻或去除的不如膜的顶部部分多,尽管事实是两者都是水平部分。这似乎是因为沟槽的纵横比太高、RF功率低和/或压力太高,故没有足够的等离子体离子轰击到达底部部分。通过操纵这些参数(例如,将纵横比改变为约2或更小),可将膜的底部部分去除或蚀刻到在膜的顶部部分中观察到的程度。
参考实施例1
在此参考实施例中,与上文实施例1中一致,证实了通过在低压下等离子体处理,杂质(碳和氮)被掺入到膜中,并且含有更多杂质的膜部分更容易受到湿法蚀刻。
以与实施例1中基本上相似的方式沉积膜(覆盖膜),然后除了如图7中所示改变处理压力外以与实施例1中基本上相似的方式将膜暴露于等离子体,随后以与实施例1中基本上相似的方式湿法蚀刻。图7为曲线图,示出了膜的处理压力[kPa]与湿法蚀刻速率(“WERR.Tox”:相对于热氧化物的湿法蚀刻速率)之间的关系。如图7中所示,与代表无等离子体处理的沉积状态的膜的“参照”相比,当处理压力为100Pa(“No.2”)时,WERR非常高(即,具有低的耐化学性的低质量膜),而当处理压力为500Pa、2,000Pa和10,000Pa时,WERR低(即,具有较高耐化学性的较高质量膜)。当处理压力高达50,000Pa(“No.1”)时,由于等离子体的离子轰击不足,故WERR增加。
另外,通过X-射线光电子能谱法(XPS)对膜进行组成分析(原子%)(在通过溅射去除每个膜的表面2nm的深度后进行分析以消除不希望的污染)。结果示于下表6中(“参考”、“No.1”和“No.2”分别对应于图7中的“参考”、“No.1”和“No.2”,并且“ND”指“未检测到”)。如表6中所示,确认杂质(碳和氮)通过低压下的等离子体处理(“No.1”)掺入到了膜中。当处理压力高达50,000Pa时(“No.2”),同无等离子体处理的膜(“参考”)一样,杂质未掺入膜中。
表6(数值为近似值)
在上文中,No.3示出了以与No.2中相同的方式、不同在于在300℃的温度下沉积SiO膜所获得的膜的数据。确认即使改变沉积条件,也可通过杂质的区域选择性掺入实现侧壁厚TS-SiO。
预示性实施例1
在此实施例中,如图3中所示进行通过杂质的区域选择性掺入实现的侧壁厚TS-SiO。以与实施例1中基本上相似的方式沉积SiO膜,如图3中的步骤S4。代替实施例1中使用的具有丙烯酸类粘合剂的聚酰亚胺胶带,在膜的沉积后,在不破坏真空的情况下,分别以约0.5slm和约2slm向腔室中引入CxHy气体(x和y为非零的整数)和Ar,以便将膜暴露于烃类气体约一分钟,从而使杂质(例如,碳)吸附到膜的表面上。其后,在与实施例1中的等离子体处理类似的条件下进行图3中的步骤S2,然后在与实施例1中类似的条件下湿法蚀刻(图3中的步骤S3)。结果,实现了具有与图6中的(c)中所示相似的拓扑的侧壁厚TS-SiO。
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 (15)
1.一种用于在衬底的表面上形成的阶梯上形成含有Si-O键的介电膜的方法,所述方法包括以下过程:
(i)通过参照初始介电膜的非目标部分预先选择待选择性去除的目标部分来设计形成在所述阶梯上的含有Si-O键的最终介电膜的拓扑,从而产生所述最终介电膜,所述目标部分为形成在所述阶梯的顶表面和底表面上的所述初始介电膜的顶部/底部部分或形成在所述阶梯的侧壁上的所述初始介电膜的侧壁部分;
(ii)在所述阶梯的所述顶表面、所述底表面和所述侧壁上保形地沉积所述初始介电膜;以及
(iii)相对于所述初始介电膜的所述非目标部分中所含的杂质的量,相对增加所述初始介电膜的所述目标部分中所含的杂质的量以获得经处理的介电膜,从而赋予所述目标部分和所述非目标部分在经受蚀刻时不同的耐化学性。
2.根据权利要求1所述的方法,所述方法还包括(iv)蚀刻所述经处理的介电膜以获得所述最终介电膜。
3.根据权利要求1所述的方法,其中所述杂质包括碳和/或卤素。
4.根据权利要求1所述的方法,其中在过程(i)中,预先选择所述侧壁部分为所述目标部分,并且在过程(ii)中,使用还含有碳和/或卤素的含硅前体沉积所述初始介电膜,并且在过程(iii)中,通过减少所述初始介电膜的所述非目标部分中所含的杂质的量来相对增加所述目标部分中所含的杂质的量,所述减少通过由在两个电极之间施加RF功率所激发的等离子体的各向异性轰击来实现,所述衬底与所述两个电极平行地放置在所述两个电极之间。
5.根据权利要求1所述的方法,其中在过程(i)中,预先选择所述顶部/底部部分为所述目标部分,并且在过程(iii)中,通过增加所述初始介电膜的所述目标部分中所含的杂质的量来相对增加所述目标部分中所含的杂质的量,所述增加通过(iiia)在所述初始介电膜的整个暴露表面上吸附含有碳和/或卤素的非硅气体和(iiib)使所述吸附了非硅气体的表面经受通过在两个电极之间施加RF功率所激发的等离子体的各向异性轰击来实现,所述衬底与所述两个电极平行地放置在所述两个电极之间。
6.根据权利要求1所述的方法,其中在过程(i)中,预先选择所述顶部/底部部分为所述目标部分,并且在过程(iii)中,通过增加所述初始介电膜的所述目标部分中所含的杂质的量来相对增加所述目标部分中所含的杂质的量,所述增加通过(iiic)使所述初始介电膜经受通过在含有碳和/或卤素的非硅气体的存在下在两个电极之间施加RF功率所激发的等离子体的各向异性轰击来实现,所述衬底与所述两个电极平行地放置在所述两个电极之间。
7.根据权利要求1所述的方法,其中在过程(ii)中,通过等离子体增强ALD或热ALD沉积所述初始介电膜。
8.根据权利要求4所述的方法,其中所述含硅前体选自Si2RyCl6-y,其中y为0至5的整数,和SiRxCl4-x,其中R为H或烷基基团,并且x为0至3的整数。
9.根据权利要求4所述的方法,其中所述RF功率为0.85W/cm2至1.41W/cm2所述衬底每单位表面积,并且在1至100Pa的压力下施加。
10.根据权利要求5所述的方法,其中所述非硅气体选自烃类气体、卤素气体和卤化气体。
11.根据权利要求5所述的方法,其中所述RF功率为0.85W/cm2至1.41W/cm2所述衬底每单位表面积,并且在1至100Pa的压力下施加。
12.根据权利要求6所述的方法,其中所述非硅气体选自烃类气体、卤素气体和卤化气体。
13.根据权利要求6所述的方法,其中所述RF功率为0.85W/cm2至1.41W/cm2所述衬底每单位表面积,并且在1至100Pa的压力下施加。
14.根据权利要求2所述的方法,其中在过程(iv)中,所述蚀刻为使用dHF的湿法蚀刻。
15.根据权利要求14所述的方法,其中所述HF的浓度为大约0.1%。
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