CN114381707A - 沉积钒金属的方法、结构、器件和沉积组件 - Google Patents
沉积钒金属的方法、结构、器件和沉积组件 Download PDFInfo
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- CN114381707A CN114381707A CN202111224369.7A CN202111224369A CN114381707A CN 114381707 A CN114381707 A CN 114381707A CN 202111224369 A CN202111224369 A CN 202111224369A CN 114381707 A CN114381707 A CN 114381707A
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- vanadium
- reaction chamber
- reducing agent
- precursor
- substrate
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 204
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 93
- 239000002184 metal Substances 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 92
- 238000000151 deposition Methods 0.000 title claims abstract description 58
- 230000008021 deposition Effects 0.000 title claims abstract description 49
- 239000002243 precursor Substances 0.000 claims abstract description 133
- 238000006243 chemical reaction Methods 0.000 claims abstract description 131
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 107
- 239000000758 substrate Substances 0.000 claims abstract description 75
- 239000007789 gas Substances 0.000 claims description 58
- -1 vanadium alkyl amide Chemical class 0.000 claims description 40
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 36
- 230000008569 process Effects 0.000 claims description 36
- 238000010926 purge Methods 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 18
- 125000004122 cyclic group Chemical group 0.000 claims description 17
- 238000005137 deposition process Methods 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
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Images
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- 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
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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
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- H01L21/04—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
- 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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
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Abstract
本公开涉及半导体器件的制造,具体涉及在衬底上形成钒金属的方法。该方法包括在反应室中提供衬底,以气相向反应室提供钒前体,并且以气相向反应室提供还原剂,以在衬底上形成钒金属。本公开还涉及由该方法形成的结构和器件,以及沉积组件。
Description
技术领域
本公开总体涉及集成电路制造领域中的半导体处理方法和系统。更具体地,本公开涉及通过沉积过程沉积钒金属和含钒金属层的方法和系统,以及包含钒金属的结构和器件。
背景技术
半导体器件例如互补金属氧化物半导体(CMOS)器件的扩展已导致集成电路的速度和密度的显著提高。然而,常规的器件扩展技术面临着未来技术节点的巨大挑战。
钒金属可能具有本领域中寻求的许多优点。然而,正电性金属的元素膜的生长本质上是具有挑战性的,已知的解决方案很少,所有这些都具有显著的局限性。它们还原成元素形式通常需要不寻常的条件或基于等离子体的方法。钒金属层属于这一类,尽管难以沉积这种材料的高质量层,但存在显著的潜在应用。
在本部分中阐述的任何讨论(包括问题和解决方案的讨论)已包括在本公开中仅是为了提供本公开的背景。这种讨论不应被视为承认任何或所有信息在本发明制造时是已知的或以其他方式构成现有技术。
发明内容
该发明内容可以简化的形式介绍一些概念,这将在下面进一步详细描述。该发明内容不一定旨在标识所要求保护的主题的关键特征或必要特征,也不旨在用于限制所要求保护的主题的范围。
钒金属层可用于例如前端线(FEOL)应用,包括作为栅极金属、作为源极/漏极接触材料、作为硅化物接触层,或者甚至作为阈值电压(Vt)调谐层中的部件。钒金属也可以在例如金属接触中用作后端线(BEOL)导电金属。它可以用作互连材料,例如作为种子层、粘合层、阻挡层或作为金属填料。
本公开的各种实施例涉及形成含钒金属材料和包含钒金属的层的方法。本公开的实施例还涉及使用这种方法形成的结构和器件,以及用于执行根据本公开的方法和/或用于形成结构和/或器件的沉积组件。总的来说,本公开的各种实施例提供了形成含钒金属材料和层的改进方法,所述含钒金属材料和层表现出本领域寻求的性能。
如本文所用,“结构”可以是或包括本文所述的衬底。结构可以包括覆盖衬底的一层或多层,比如根据根据本公开的方法形成的一层或多层。
在本公开中,变量的任意两个数字可以构成该变量的可行范围,并且指示的任何范围可以包括或排除端点。此外,指示的变量任何值(不管它们是否用“约”指示)可以指精确值或近似值,并且包括等同物,并且可以指平均值、中值、代表性、多数等。此外,在本公开中,在一些实施例中,术语“包括”、“由…构成”和“具有”独立地指“通常或广泛地包括”、“包含”、“基本由…构成”或“由…构成”。在本公开中,在一些实施例中,任何定义的含义不一定排除普通和习惯含义。
附图说明
所包括的附图用于提供对本公开的进一步理解并构成本说明书的一部分,附图示出了示例性实施例,并与描述一起帮助解释本公开的原理。在图中:
图1A和1B示出了根据本公开的方法的实施例。
图2以示意方式描绘了根据本公开的包括含钒金属层的结构。
图3以示意方式呈现了根据本公开的沉积设备。
具体实施方式
下面提供的方法、结构、器件和设备的示例性实施例的描述仅仅是示例性的且仅是为了说明的目的。以下描述不旨在限制本公开或权利要求的范围。此外,具有所述特征的多个实施例的叙述并不旨在排除具有附加特征的其他实施例或包含所述特征的不同组合的其他实施例。例如,各种实施例被阐述为示例性实施例,并且可以在从属权利要求中陈述。除非另有说明,示例性实施例或其部件可以组合或者可以彼此分开应用。
本公开涉及一种在衬底上沉积钒金属的方法。该方法包括在反应室中提供衬底,以气相在反应室中提供钒前体,以及以气相向反应室提供还原剂,以在衬底上形成钒金属。在本公开中,钒主要或在一些实施例中基本完全或完全作为元素金属沉积。因此,在一些实施例中,钒的氧化态为零。
在一些实施例中,钒金属作为含钒金属层沉积。如本文所用,“含钒金属层”可以是包含元素形式的钒的材料层。因此,钒的氧化态可能为零。含钒金属层可以包括额外的元素,比如氧等。在一些实施例中,含钒金属层可以包括相当大比例的除钒之外的其他元素。因此,含钒金属层包括钒金属、基本由其或由其构成。
在一些实施例中,含钒金属层可以是种子层。种子层可用于增强另一层的沉积。种子层可以包括两种金属以形成二元合金,或者三种金属以形成三元合金,或者四种金属以形成四元合金。可以选择合金成分来优化种子层的抗氧化性、粘附性或其他性能。合金中使用的金属可以包括但不限于锆、铬、钛和钌。在一些实施例中,可以使用其他过渡金属来替代或补充上述金属。钒合金的示例是不同比例的钒铬、钒钛和钒钌。
如本文所用,术语“层”和/或“膜”可以指任何连续或非连续的结构和材料,比如通过本文公开的方法沉积的材料。例如,层和/或膜可以包括二维材料、三维材料、纳米颗粒或甚至部分或全部分子层或部分或全部原子层或原子和/或分子簇。膜或层可以包括具有针孔的材料或层,针孔可以至少部分连续。种子层可以是用于增加另一种材料成核速率的非连续层。然而,种子层也可以基本或完全连续。
在一些实施例中,含钒金属层可以包括例如钒的80、90、95或99原子百分比(原子%)。在一些实施例中,含钒金属层可以基本由或者由钒构成。在一些实施例中,含钒金属层可以基本由或者由钒金属构成。由钒金属构成的层可以包括可接受量的杂质,比如氧、碳、氯或其他卤素,和/或氢,其可以来源于用于沉积含钒金属层的一种或多种前体。如本文所用,钒金属是指钒的元素形式,即氧化态为零的钒元素。
在一些实施例中,含钒金属层的钒含量为从至少1.0原子百分比(原子%)到至多99.5原子%,或从至少3.0原子%到至多97.0原子%,或从至少5.0原子%到至多95.0原子%,或从至少10.0原子%到至多90.0原子%,或从至少20.0原子%到至多80.0原子%,或从至少30.0原子%到至多70.0原子%,或从至少40.0原子%到至多60.0原子%。
在一些实施例中,含钒金属层可以包含从0.05原子百分比(原子%)到99.0原子%,或从3.0原子%至97.0原子百分比,或从5.0原子百分比至95.0原子百分比,或从10.0原子百分比至90.0原子百分比,或从20.0原子百分比至80.0原子百分比,或从30.0原子百分比至70.0原子百分比,或从40.0原子百分比至60.0原子百分比氧和/或碳和/或氮和/或其他附加元素。
衬底可以是可用于形成或可在其上形成结构、器件、电路或层的任何一种或多种底层材料。衬底可以包括块体材料,比如硅(例如单晶硅)、其他第四族材料,比如锗,或者其他半导体材料,比如第二-第六族或第三-第五族半导体材料,并且可以包括在块体材料之上或之下的一个或多个层。此外,衬底可以包括各种特征,比如形成在衬底层的至少一部分之内或之上的凹陷、突起等。例如,衬底可以包括块体半导体材料和覆盖块体半导体材料的至少一部分的绝缘或介电材料层。衬底可以包括氮化物,例如TiN、氧化物、绝缘材料、介电材料、导电材料、金属,比如钨、钌、钼或铜,或者金属材料、晶体材料、外延材料、异质外延材料和/或单晶材料。在本公开的一些实施例中,衬底包括硅。如上所述,除了硅之外,衬底可以包括其他材料。其他材料可以形成层。
根据本公开的沉积钒金属的方法包括在反应室中提供衬底。换句话说,将衬底带入可以控制沉积条件的空间。反应室可以是组合工具的一部分,其中执行不同的过程以形成集成电路。在一些实施例中,反应室可以是流动型反应器,例如错流反应器。在一些实施例中,反应室可以是喷淋头反应器。在一些实施例中,反应室可以是空间分隔的反应器。在一些实施例中,反应室可以是单晶片ALD反应器。在一些实施例中,反应室可以是大批量制造的单晶片ALD反应器。在一些实施例中,反应室可以是用于同时制造多个衬底的分批反应器。
术语“前体”和“反应物”可以指参与产生另一种化合物的化学反应的分子(化合物或包含单一元素的分子)。前体通常包含至少部分结合到由所讨论的化学反应产生的化合物或元素中的部分。这样得到的化合物或元素可以沉积在衬底上。反应物可以是没有在很大程度上结合到所得的化合物或元素中的元素或化合物。还原剂可以是反应物。
术语“惰性气体”可以指不参与化学反应和/或在相当程度上不成为层的一部分的气体。示例性惰性气体包括He和Ar及其任意组合。在一些情况下,分子氮和/或氢可以是惰性气体。除了惰性气体和参与反应的气体(统称为“处理气体”)之外,处理环境可能包含其他气体。例如,除了处理气体之外的气体,即没有通过前体注射器系统、其他气体分配装置等引入的气体,可以用于例如密封反应空间,并且可以包括密封气体。
如本文所用,“钒前体”包括可以变成气态的气体或材料,其可以由包括钒的化学式表示,例如卤化钒、钒烷基酰胺化合物和钒脒化合物中的一种或多种。钒前体可以是有机或无机分子。在一些实施例中,钒前体以两种或更多种化合物的混合物形式提供。在混合物中,除钒前体之外的其它化合物可以是惰性化合物或元素。在一些实施例中,钒前体以组合物的形式提供。
适合用作组合物的组合物可以包括钒化合物和有效量的一种或多种稳定剂。组合物可能是溶液。稳定剂能够或能够促进减少钒前体的不希望的热分解,例如在钒前体的运输或储存期间可能发生的分解。在一些实施例中,稳定剂可以与钒前体结合和/或形成加合物,和/或包括稳定钒前体的溶剂。稳定剂可以包括形成加合物的化合物。稳定剂可以包括非质子化合物。稳定化合物可以例如包含带有能够与钒形成配位键(配价键)以形成加合物的孤对电子的一个或多个杂原子。稳定剂可以选择成不影响钒前体蒸汽或钒前体加合物蒸汽的输送,或者尽量减少稳定剂作为杂质混入含钒金属层。稳定剂的加入量可以从微量的“催化抑制剂”量到1:1的化学计量。期望的比率可以取决于例如特定的钒前体和期望的稳定程度。
一种或多种稳定剂可以与钒前体一起使用。一种或多种稳定剂中的至少一种可以是或包括有机分子。有机分子可以包括氮、氧、硫和/或氧杂原子中的一种或多种。一种或多种稳定剂中的至少一种可以选自式NR3的叔胺,其中所有-R基团独立地是C1-C20烷基或C1-C20芳基;式PR3的叔膦,其中所有-R基团独立地是C1-C20烷基或C1-C20芳基;式OR2的醚,其中所有-R基团独立地是C1-C20烷基或C1-C20芳基;式SR2的二烷基硫化物、二芳基硫化物或混合烷基/芳基硫化物,其中所有-R基团独立地是C1-C20烷基或C1-C20芳基;芳族杂环胺,例如吡啶、哒嗪、嘧啶、吡嗪或1,2,4-三嗪,及其烷基或芳基取代形式;非质子非芳族杂环胺,例如N-烷基哌啶、N,N'-二烷基哌嗪、N-烷基吡咯烷、N-烷基吡咯烷、N-烷基吡咯烷、N,N'-二烷基咪唑烷和类似化合物,其中烷基可以是C1-C20烃基;杂环醚,例如呋喃、四氢呋喃、吡喃、四氢吡喃、1,4-二恶烷、1,4-二恶烷和类似化合物,及其烷基或芳基取代形式;杂环硫醚,例如噻吩、四氢噻吩、噻唑、噻烷、噻吡喃、二噻烷和类似化合物,及其普通烷基或芳基取代形式等。溶液或组合物可以包括任何合适数量的稳定剂,例如两种或更多种稳定剂,其中两种或多种稳定剂中的一种或多种可以选自上面的列表。两种或更多种稳定剂可以包括两种或更多种稳定剂的任意组合,包括来自上述示例的至少一种稳定剂。
根据本公开的示例,组合物在常温常压下可以是液体或气体。
在一些实施例中,钒前体包括无机化合物。在一些实施例中,钒前体包括卤化钒或卤氧化钒。卤化钒可以是或包括氯化钒,例如四氯化钒。在一些实施例中,钒前体包括氟化钒、氯化钒、溴化钒、碘化钒、氟氧化钒、氯氧化钒、溴氧化钒或碘氧化钒。在一些实施例中,钒前体选自VCl4和VOCl3。
在一些实施例中,钒前体包含有机化合物。有机钒前体可以包含钒烷基酰胺基化合物或钒二烷基酰胺基化合物。有机钒前体可以包含脒化钒、钒醇盐和氧钒醇盐、β-二酮钒以及钒环戊二烯基化合物。在一些实施例中,钒前体包含V(NMe2)4、V(NEt2)4和/或V(NEtMe)4。
在根据本公开的方法中,当钒前体在反应室中时,它可以处于气相。钒前体在被提供到反应室之前的某些时间点可以是部分气体或液体,或者甚至是固体。换句话说,钒前体可以是固体、液体或气体,例如在输送到反应室之前在前体容器或其它容器中。当输送到反应室中时,可以应用使前体成为气相的各种方法。这样的方法可以包括例如加热器、蒸发器、气流或施加较低压力,或它们的任意组合。
在本公开中,“气体”可以包括在常温常压(NTP)下为气体、蒸发的固体和/或蒸发的液体的材料。根据情况,气体可以由单一气体或气体混合物构成。钒前体可以气相形式提供给反应室。
在根据本公开的方法中,还原剂以气相提供给反应室,以在衬底上形成钒金属。术语“还原剂”可以指能够变成气态并且能够将钒前体还原成钒金属的气体或材料。还原剂可以气相形式提供给反应室。在根据本公开的方法中,还原剂可以与包含化学吸附的钒前体的衬底接触。钒前体向钒金属的还原可以发生在衬底表面。在一些实施例中,还原可以至少部分地在气相中进行。将钒前体和还原剂引入反应室可以至少部分地重叠。在一些实施例中,将钒前体和还原剂引入反应室可以同时进行。然而,在一些实施例中,将钒前体和还原剂引入反应室可以至少部分地分开。
根据本公开的还原剂可以包括氢。在一些实施例中,根据本公开的还原剂包括分子氢(H2)或源自H2的等离子体。根据本公开的还原剂可以包括硼。在一些实施例中,还原剂包括、基本由或由乙硼烷(B2H6)或硼烷(BH3)的中性配体加合物构成。
在一些实施例中,根据本公开的还原剂包括氮。在一些实施例中,还原剂可以包括、基本由或由肼或其衍生物构成。在一些实施例中,还原剂可以包括烷基肼或二烷基肼。在一些实施例中,还原剂可以包括二氮烯基化合物。二氮烯基化合物可以是偶氮-叔丁烷。在一些实施例中,还原剂可以包括、基本由或由以下构成:1,1-二乙基肼、1-乙基-1-甲基肼、异丙基肼、苯肼、1,1-二苯基肼、1,2-二苯基肼、N-氨基哌啶、N-氨基吡咯烷、N-氨基吡咯烷、N-甲基-N-苯肼、1-氨基-1,2,3,4-四氢喹啉、N-氨基哌嗪、1,1-二苄基肼、1,2-二苄基肼、1-乙基-1-苯肼、1-氨基氮杂环己烷、1-甲基-1-(间甲苯基)肼、1-乙基-1-(对甲苯基)肼、1-氨基咪唑、1-氨基-2,6-二甲基哌啶、N-氨基苯胺或偶氮-叔丁烷。
还原剂可以包括、基本由或由一种或多种烃取代肼还原剂构成。在本公开的一些实施例中,方法可以包括选择取代肼以包含烷基。每个烷基可以包含一个或多个比如两个、三个、四个、五个、六个、七个或八个碳原子。取代肼还原剂中烷基的数量可以是一个、两个、三个或四个。出于本公开的目的,烷基可以是芳基。因此,根据本公开的还原剂可包括例如酚肼或二酚肼。
在本公开中,“烷基”是指包含至少一个碳原子的饱和或不饱和烃链,比如但不限于甲基、乙基、丙基、丁基、戊基、己基、庚基和辛基及其异构体,比如n-、异-、仲-和叔-异构体。烷基可以是直链、支链或环状的,并且可以包括烷基的所有结构异构体形式。烷基可被取代。烷基的取代基可以是单个原子比如卤素或官能团比如羟基。在本公开的一些实施例中,烷基肼可以包括键合到氮上的至少一个氢。在本公开的一些实施例中,烷基肼可以包含键合到氮上的至少两个氢。在本公开的一些实施例中,烷基肼可以包含键合到氮上的至少一个氢和键合到氮上的至少一个烷基链。在本公开的一些实施例中,烷基肼可以包括叔丁基肼(C4H9N2H3)、二甲基肼(比如1,1-二甲基肼、1,2-二甲基肼)或二乙基肼中的一种或多种。在本公开的一些实施例中,取代肼具有附接到氮上的至少一个烃基。在本公开的一些实施例中,取代肼具有附接到氮上的至少两个烃基。在本公开的一些实施例中,取代肼具有附接到氮上的至少三个烃基。在本公开的一些实施例中,取代肼具有附接到氮上的至少一个C1-C3烃基。例如,烷基肼可以包括附接到氮原子上的一个C1-C3烷基,或者烷基肼可以包括附接到两个氮原子上的一个C1-C3烷基,或者烷基肼可以包括附接到一个氮原子上的两个C1-C3烷基,或者烷基肼可以包括附接到两个氮原子上的两个C1-C3烷基。在本公开的一些实施例中,烷基肼具有附接到氮上的至少一个C4-C10烷基。例如,烷基肼可以包括附接到氮原子上的一个C4-C10烷基,或者烷基肼可以包括附接到两个氮原子上的一个C4-C10烷基,或者烷基肼可以包括附接到一个氮原子上的两个C4-C10烷基,或者烷基肼可以包括附接到两个氮原子上的两个C4-C10烷基。
取代肼可以包含芳族取代基。取代肼可以包含附接到氮原子上的一个、两个、三个或四个芳族取代基。在一些实施例中,取代肼包含附接到氮原子上的一个芳族取代基。在一些实施例中,取代肼包含两个芳族取代基。两个芳族取代基可以附接到相同或不同的氮原子上。在一些实施例中,取代肼包含三个芳族取代基,且在一些实施例中,取代肼包含四个芳族取代基。每个芳族取代基可以独立地被一个或多个取代基取代,包括单个原子或官能团。在一些实施例中,取代肼可以包含一个或多个烷基和一个或多个芳族取代基。
在本公开的一些实施例中,取代肼具有附接到氮上的直链、支链或环状或芳族烃基。在本公开的一些实施例中,取代肼包括附接到氮上的取代烃基。
在本公开的一些实施例中,取代肼具有下式:
RIRII-N-NRIIIRIV (1)
在根据式(1)的取代肼中,RI可以选自烃基,例如直链、支链、环状、芳族或取代烃基,并且RII,RIII,RIV基团中的每个可以独立地选自氢或烃基,例如直链、支链、环状、芳族或取代烃基。
在根据式(1)的取代肼的一些实施例中,RI,RII,RIII,RIV中的每个可以是C1-C10烃、C1-C3烃、C4-C10烃或氢,例如直链、支链、环状、芳香族或取代烃基。在一些实施例中,RI,RII,RIII,RIV基团中的至少一个包括芳基,例如苯基。在一些实施例中,RI,RII,RIII,RIV基团中的至少一个包括甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基或苯基。在一些实施例中,每个RI,RII,RIII,RIV基团中的至少两个可以独立地选择为包括甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基或苯基。在一些实施例中,RII,RIII,RIV基团是氢。在一些实施例中,RII,RIII,RIV基团中的至少两个是氢。在一些实施例中,RII,RIII,RIV基团中的至少一个是氢。在一些实施例中,所有的RII,RIII,RIV基团都是烃。
根据本公开的还原剂可以包括铝。在一些实施例中,还原剂包括氢化铝(AlH3)或氢化铝的中性配体加合物。在一些实施例中,还原剂包括含有Al-H键的氨基络合物或含有Al-H键的酰胺络合物。在一些实施例中,还原剂包括有机金属化合物。在一些实施例中,有机金属化合物包括铝。有机金属化合物可以包括、基本由或由三甲基铝、三乙基铝、三异丙基铝、三叔丁基铝或氢化二异丁基铝构成。
在一些实施例中,还原剂包括有机分子,即还原剂可以是有机还原剂。有机还原剂可以包括羧酸,例如甲酸或草酸。有机还原剂可以包括醛,例如甲醛或乙二醛。有机还原剂可以包含1,2-二亚胺或1,2-二亚胺的金属配合物。
在本公开中,沉积过程可以包括循环沉积过程,例如原子层沉积(ALD)过程或循环化学气相沉积(CVD)过程。术语“循环沉积过程”可以指将前体和/或还原剂顺序引入反应室,以在衬底上沉积材料,例如含钒金属材料。循环沉积包括诸如原子层沉积(ALD)、循环化学气相沉积(循环CVD)和包括ALD成分和循环CVD成分的混合循环沉积过程的处理技术。过程可以包括在反应室中提供前体之间或提供前体和还原剂之间的吹扫步骤。
过程可以包括一个或多个循环阶段。在一些实施例中,过程包括一个或多个无环阶段。在一些实施例中,沉积过程包括至少一种前体的连续流动。在一些实施例中,还原剂可以连续提供在反应室中。在这样的实施例中,过程包括还原剂的连续流动。在一些实施例中,根据本公开的方法包括在反应室中交替和顺序地提供钒前体和还原剂,并且在反应室中提供钒前体和还原剂之间吹扫反应室。
术语“原子层沉积”(ALD)可以指气相沉积过程,其中沉积循环比如多个连续的沉积循环在反应室中进行。本文使用的术语原子层沉积也意味着包括由相关术语指定的过程,例如化学气相原子层沉积,当用前体/反应气体和可选的吹扫气体的交替脉冲执行时。通常,对于ALD过程,在每个循环期间,前体被引入反应室,并被化学吸附到沉积表面(例如可以包括来自先前ALD循环的先前沉积的材料或其他材料的衬底表面),形成不容易与额外前体反应的材料的单层或亚单层(即自限制反应)。此后,在一些情况下,可以随后将反应物(例如另一种前体或反应气体)引入处理室,用于将化学吸附的前体转化为沉积表面上的所需材料。反应物能够与前体进一步反应。在一个或多个循环期间,例如在每个循环的每个步骤期间,可以利用吹扫步骤来从处理室去除任何过量的前体和/或从反应室去除任何过量的反应物和/或反应副产物。反应物可以是还原剂。
CVD型过程通常涉及两种或更多种前体和/或反应物之间的气相反应。前体和/或反应物可以同时提供给反应空间或衬底,或者以部分或完全分离的脉冲。衬底和/或反应空间可被加热以促进气态反应物之间的反应。在一些实施例中,提供反应物,直到沉积具有期望厚度的层。在一些实施例中,循环CVD过程可以与多个循环一起使用,以沉积具有期望厚度的薄膜。在循环CVD过程中,反应物可以不重叠或部分或完全重叠的脉冲提供给反应室。
在一些实施例中,钒前体、还原剂或两者以脉冲提供给反应室。钒前体或还原剂脉冲的长度可以是例如约0.01秒至约60秒,例如约0.01秒至约5秒,或约5秒至约10秒,或约10秒至约30秒,或约10秒至约60秒,或约20秒至约60秒。合适的脉冲时间的选择可以取决于衬底拓扑。对于更高纵横比结构,可能需要更长脉冲时间来在高纵横比结构的不同区域中获得足够的表面饱和度。出于过程优化的目的,只要能够获得足够的层质量,较短脉冲时间可能是优选的。例如,钒前体或还原剂脉冲的长度可以是约0.01秒、0.03秒、0.05秒、0.1秒、0.2秒、0.5秒、1秒、1.5秒、2秒、2.5秒、3秒、4秒、5秒、7秒、10秒、12秒、14秒或16秒。在一些实施例中,钒前体或还原剂脉冲时间可以为约15至约20秒,或约15至约30秒,或约15至约25秒,例如18秒、22秒、26秒或28秒或31秒。在一些实施例中,钒前体或还原剂的脉冲时间可以从约10秒到约60秒,从约30秒到约60秒,并且脉冲时间可以是例如约25秒、35秒、45秒或50秒。在某些实施例中,几分钟范围内的脉冲时间可以用于钒前体和还原剂。钒前体和还原剂的脉冲时间根据所讨论的过程而独立变化。在一些实施例中,钒前体脉冲时间比还原剂脉冲时间长。在一些实施例中,还原剂脉冲时间比钒前体脉冲时间长。在一些实施例中,钒前体脉冲时间与还原剂脉冲时间相同。
在一些实施例中,在还原剂被脉冲到反应室之前,钒前体可被脉冲不止一次,例如两次、三次或四次。类似地,在钒前体被脉冲(即提供)到反应室之前,还原剂可以有一个以上脉冲,例如两个、三个或四个脉冲。在一些实施例中,在每个脉冲之间有吹扫步骤。因此,反应室也可以在相同化学物质比如钒前体或还原剂的两个脉冲之间被吹扫。
在衬底上脉冲钒前体的过程中,钒前体的流量可以小于2000sccm,或小于1000sccm,或小于500sccm,或小于100sccm。钒前体流量可以是例如从500sccm到1200sccm,例如600sccm、800sccm或1000sccm。该时间段可以根据所讨论的钒前体和其他过程参数而变化,这些参数可以根据所讨论的应用来选择。
在一些实施例中,该方法包括在反应室中提供还原剂之前通过惰性气体从反应室中除去过量的钒前体。在一些实施例中,在反应室中提供钒前体和在反应室中提供还原剂之间吹扫反应室。
如本文所用,术语“吹扫”可以指过程:其中例如通过用真空泵抽空反应室和/或通过用惰性或基本惰性气体比如氩或氮替换反应室内的气体,从衬底表面除去气相前体和/或气相副产物。吹扫可以在相互反应的两种气体脉冲之间进行。然而,吹扫可以在相互不反应的两种气体脉冲之间进行。例如,可在两种前体的脉冲之间或前体和还原剂之间提供吹扫。吹扫可以避免或至少减少相互反应的两种气体之间的气相相互作用。应当理解,吹扫可以在时间上或空间上或者这两者上进行。例如,在暂时吹扫的情况下,可例如以以下时间顺序使用吹扫步骤:向反应室提供第一前体、向反应室提供吹扫气体和向反应室提供第二前体,其中其上沉积有层的衬底不移动。例如,在空间吹扫的情况下,吹扫步骤可以采取以下形式:通过吹扫气幕将衬底从第一前体被连续供应到的第一位置移动到第二前体被连续供应到的第二位置。吹扫时间可以是例如约0.05至约20秒,或约0.2至约10秒,或约0.5至约5秒。然而,如果需要,可以使用其他吹扫时间,例如在需要在极高纵横比结构或具有复杂表面形态的其他结构上高度共形的台阶覆盖的情况下,或者在使用不同反应器类型比如分批反应器的情况下。
在一些实施例中,根据本公开的方法包括热沉积过程。在热沉积中,与环境温度相关的温度升高会促进化学反应。通常,温度升高提供在没有其它外部能源比如等离子体、自由基或其它形式辐射的情况下形成钒金属所需的能量。在一些实施例中,根据本公开的方法部分或完全是等离子体增强沉积方法,例如PEALD或PECVD。
在一些实施例中,向反应室提供还原剂的持续时间(即还原剂脉冲时间)大于或等于约5秒,或大于或等于约10秒,或大于或等于约30秒,或约5秒至约10秒,或约10秒至约60秒。在一些实施例中,向反应室提供还原剂的持续时间小于约20秒、小于约10秒、小于约5秒、小于约2秒或小于约0.1秒。在一些实施例中,还原剂脉冲时间在约0.1秒和15秒之间,或者在约0.1秒和5秒之间,或者在约0.1秒和3秒之间,或者在约5秒和15秒之间,或者在约7秒和10秒之间。
在一些实施例中,向反应室提供还原剂包括在衬底上脉冲还原剂。在还原剂在衬底上脉冲的实施例中,还原剂可以脉冲以下时间段:0.1秒至2.0秒或约0.01秒至约10秒或小于约60秒,或小于约30秒,或小于约20秒,小于约10秒或小于约5秒。在还原剂在衬底上脉冲期间,还原剂的流量可以小于2000sccm,或小于1000sccm,或小于500sccm,或小于100sccm。还原剂流量可以是例如500sccm至1200sccm,例如600sccm、800sccm或1000sccm。该时间段可以根据所讨论的还原剂和其他过程参数而变化,这些参数可以根据所讨论的应用来选择。
在一些实施例中,钒金属可以在约20℃至约800℃的温度下沉积。例如,钒金属可以在约20℃至约450℃的温度例如约50℃至约450℃下或者在约450℃至约800℃的温度下沉积。在本公开的一些实施例中,钒金属可以在约20℃至约300℃的温度下或者在约300℃至约600℃的温度下沉积。在一些实施例中,钒金属可以在约50℃至约150℃的温度下或者在约350℃至约400℃的温度下或者在约500℃至约700℃的温度下沉积。例如,钒金属可以在以下温度下沉积:约75℃或约125℃,或约175℃,或约225℃,或约250℃或约325℃,或约375℃,或约550℃,或约650℃,或约750℃。
在一些实施例中,沉积过程中反应室内的压力小于760托,或者其中沉积过程中反应室内的压力在0.2托和760托之间,或者在1托和100托之间,或者在1托和10托之间。在一些实施例中,钒金属的沉积在小于约0.001托、小于0.01托、小于0.1托、小于10托或小于50托的压力下进行。在一些实施例中,在根据本公开的方法的至少一部分期间,反应室的压力小于约0.001托、小于0.01托、小于0.1托、小于10托或小于50托。
在一方面,公开了含钒金属层。根据本公开的含钒金属层包括根据本文描述的过程沉积的钒金属。
在另一方面,公开了包括根据本文所述过程生产的含钒金属层的结构。
在又一方面,公开了包括根据本文所述过程生产的含钒金属层的器件。
在另一方面,公开了用于在衬底上沉积元素钒的沉积组件。沉积组件包括构造和布置成保持衬底的一个或多个反应室,以及构造和布置成向反应室中提供钒前体和/或还原剂的前体注射器系统。沉积组件包括构造和布置成容纳和蒸发钒前体的前体容器,并且该组件构造和布置成通过前体注射器系统向反应室提供前体,以在衬底上沉积元素钒。
图1A和1B示出了根据本公开的示例性实施例的方法100。方法100可用于形成包含钒金属的层,即含钒金属层。含钒金属层可在结构或器件比如本文所述的结构或器件的形成过程中使用。然而,除非另有说明,方法不限于这种应用。
在步骤102期间,将衬底提供到反应器的反应室中。反应室可以形成原子层沉积(ALD)反应器的一部分。反应器可以是单晶片反应器。可替代地,反应器可以是分批反应器。方法100的各个阶段可以在单个反应室中进行,或者它们可以在多个反应器室中进行,例如组合工具的反应室。在一些实施例中,方法100在组合工具的单个反应室中进行,但结构或器件的其他、之前或之后的制造步骤在同一组合工具的附加反应室中进行。可选地,包括反应室的反应器可以设置有加热器,以通过升高一种或多种衬底和/或反应物和/或前体的温度来激活反应。
在步骤102期间,可以使衬底达到期望的温度和压力,用于在反应室104中提供钒前体和/或在反应室106中提供还原剂。反应室内的温度(例如衬底或衬底支架的温度)可以是例如约50℃至约500℃,或约250℃至约750℃。作为另一示例,反应室内的温度可以是约20℃至约300℃,或约400℃至约8000℃。反应室内的示例性温度是75℃、125℃、225℃、275℃、350℃、550℃和700℃。
反应室内的压力可以小于760托、小于500托、小于100托、小于50托或小于20托、小于5托、小于1托或小于0.1托。
钒前体被提供在包含衬底的反应室104中。在不将本公开限制于任何特定理论的情况下,在反应室104中提供钒前体期间,钒前体可以化学吸附在衬底上。在反应室中提供钒前体的持续时间(钒前体脉冲时间)可以是例如0.01秒、0.1秒、0.5秒、1秒、1.5秒、2秒、2.5秒、3秒、3.5秒、4秒、5秒或5秒、10秒、20秒、40秒或60秒。在一些实施例中,在反应室中提供钒前体的持续时间(钒前体脉冲时间)可以大于5秒或大于10秒或大于约30秒,例如约45秒。在一些实施例中,钒前体脉冲时间可以短于15秒。
当还原剂被提供在反应室106中时,它可以与化学吸附的钒前体或其衍生物质反应以形成钒金属。在反应室中提供还原剂的持续时间(还原剂脉冲时间)可以是例如0.01秒、0.1秒、0.5秒、1秒、2秒、3秒、4秒、5秒、7秒、8秒、9秒、10秒、15秒、20秒、30秒或45秒。在一些实施例中,在反应室中提供还原剂的持续时间小于15秒或小于10秒或约3秒。然而,在一些实施例中,在反应室中提供还原剂的持续时间长于15秒、长于30秒或长于45秒,例如约50秒或60秒。
以任何顺序执行的阶段104和106可以形成沉积循环,导致钒金属的沉积。在一些实施例中,可以重复(环108)钒金属沉积的两个阶段,即在反应室中提供钒前体和还原剂(104和106)。这样的实施例包含多个沉积循环。沉积的钒金属的厚度可以通过调节沉积循环的次数来调整。沉积循环(环108)可以重复,直到获得期望的钒金属厚度。例如可以进行2至约2000例如约10至约2000、约50至约2000或约500至约2000个沉积循环。在一些实施例中,可以进行2至约10、或2至约50、或2至约100、或2至约200、或2至约500、或2至约1000个沉积循环。例如,可以执行约2、5、10、50或100个沉积循环。在一些实施例中,可以执行约150、200、250、300、400、500、600、700、800、900、1200或1500个沉积循环。
在一个循环中沉积的钒金属量(每个循环的生长量,GPC)根据处理条件而变化,并且可以是从约到约例如从约到约或者从约到约在一些实施例中,GPC可为约至约或约至约在一些实施例中,GPC可以是例如 或或取决于沉积条件、沉积循环数等,可以沉积不同厚度的钒金属或含钒金属层。例如,钒金属或含钒金属层的厚度可以在约0.3nm和50nm之间,例如约0.5nm、1nm、1.5nm、2nm、2.5nm、3nm、3.5nm、4nm、4.5nm、5nm、6nm、7nm、8nm、10nm、15nm、20nm或25nm。在一些实施例中,钒金属或含钒金属层可以具有约30nm、40nm或50nm的厚度。期望的厚度可以根据所讨论的应用来选择。例如,填充应用可以利用比例如衬垫或空间有限的其他层更厚的层。
钒前体和还原剂可以在单独的步骤(104和106)中提供在反应室中。图1B示出了根据本公开的实施例,其中步骤104和106由吹扫步骤105和107分开。在这样的实施例中,沉积循环包括一个或多个吹扫步骤103、105。在吹扫步骤期间,前体和/或还原剂可以通过惰性气体比如氩(Ar)、氮(N2)或氦(He)和/或真空压力而暂时彼此分开。
吹扫反应室103、105可以防止或减轻钒前体和还原剂之间的气相反应,并实现自饱和表面反应。多余的化学物质和反应副产物(如果有的话)可以在衬底与下一种反应性化学物质接触之前从衬底表面去除,例如通过吹扫反应室或通过移动衬底。然而,在一些实施例中,可以移动衬底以分别接触钒前体和还原剂。因为在一些实施例中,反应可能自饱和,所以可能不需要对衬底进行严格的温度控制和对前体进行精确的剂量控制。然而,衬底温度优选使得入射气体物质不会冷凝成单层或多单层,也不会在表面上热分解。
当执行方法100时,钒金属沉积在衬底上。沉积过程可以是循环沉积过程,并且可以包括循环CVD、ALD沉积或混合循环CVD/ALD沉积过程。例如,在一些实施例中,与CVD过程相比,特定ALD过程的生长速率可能较低。一种提高生长速率的方法可以是在比ALD过程中通常采用的沉积温度更高的沉积温度下操作,得到化学气相沉积过程的某些部分,但仍利用钒前体和还原剂的顺序引入。这种过程可以称为循环CVD。在一些实施例中,循环CVD过程可以包括将两种或更多种前体引入反应室,其中在反应室中的两种或更多种前体之间可以有重叠时间段,得到沉积的ALD成分和沉积的CVD成分。这被称为混合过程。根据进一步的示例,循环沉积过程可以包括一种还原剂或前体的连续流动和另一种化学成分进入反应室的周期性脉冲。步骤104期间反应室内的温度和/或压力可以与上面结合步骤102提到的任何压力和温度相同或相似。
图2示出了根据本公开的示例性结构或器件200的一部分。器件或结构200的一部分包括衬底202、钒层204和在衬底202和含钒金属层204之间(例如与一个或两者接触)的可选底层206。衬底202可以是或包括本文描述的任何衬底材料,例如电介质或绝缘层。举例来说,电介质或绝缘层可以是高k材料,例如介电常数大于约7的金属氧化物。在一些实施例中,高k材料的介电常数高于氧化硅的介电常数。示例性高k材料包括氧化铪(HfO2)、氧化钽(Ta2O5)、氧化锆(ZrO2)、氧化钛(TiO2)、硅酸铪(HfSiOx)、氧化铝(Al2O3)、氧化镧(La2O3)、氮化钛以及包括一个或多个这种层的混合物/层压材料中的一种或多种。
含钒金属层204可以根据本文描述的方法形成。当使用循环沉积过程形成底层206时,底层206成分(例如过渡金属、C、S或N)的浓度可以从底层206的底部到底层206的顶部变化,例如通过在一个或多个沉积循环期间控制前体和/或反应物的量和/或相应的脉冲时间。底层可以是种子层。
在一些实施例中,含钒金属层可以直接沉积在衬底上。在这样的实施例中,没有底层。作为进一步替代,根据本公开的结构或器件可以包括在衬底和含钒金属层之间的附加层。此外,在一些实施例中,含钒层沉积在衬底上,并且至少一个附加层沉积在含钒层上。在一些进一步实施例中,根据本公开的含钒层可以在其它层的沉积中用作种子层。
在一些实施例中,含钒金属层204可以基本由或者由钒金属构成。
根据本公开示例的结构和器件可以包括水平结构、竖直和/或三维结构和器件,比如鳍式FET器件、栅极环绕器件和纳米片器件。
图3以示意方式示出了根据本公开的沉积组件300。沉积组件300可用于执行本文所述的方法和/或形成本文所述的结构或器件或其一部分。
在图示的示例中,沉积组件300包括一个或多个反应室302、前体注射器系统301、钒前体容器304、还原剂容器306、吹扫气体源308、排气源310和控制器312。
反应室302可以包括任何合适的反应室,例如ALD或CVD反应室。
钒前体容器304可以包括容器和如本文所述的一种或多种钒前体—单独或与一种或多种载体(例如惰性)气体混合。还原剂容器306可以包括容器和本文所述的一种或多种还原剂—单独或与一种或多种载气混合。吹扫气体源308可以包括如本文所述的一种或多种惰性气体。尽管图示了三个源容器304-308,但沉积组件300可以包括任何合适数量的源容器。源容器304-308可以通过管线314-318联接到反应室302,每个管线可以包括流量控制器、阀、加热器等。
排气源310可以包括一个或多个真空泵。
控制器312包括电子电路和软件,以选择性地操作沉积组件300中包括的阀、歧管、加热器、泵和其他部件。这种电路和部件操作成从相应源304-308引入前体、还原剂和吹扫气体。控制器312可以控制气体脉冲序列的定时、衬底和/或反应室302的温度、反应室302内的压力以及各种其他操作,以提供沉积组件300的正确操作。控制器312可以包括控制软件,以电动或气动地控制阀来控制前体、还原剂和吹扫气体流入和流出反应室302。控制器312可以包括执行特定任务的模块,例如软件或硬件部件。模块可以配置为驻留在控制系统的可寻址存储介质上,并且配置为执行一个或多个过程。
沉积组件300的其他配置也是可能的,包括不同数量和种类的前体和还原剂源以及吹扫气体源。此外,应当理解,有许多阀、导管、前体源和吹扫气体源的布置可用于实现以选择性和协调的方式将气体供给到反应室302中的目标。此外,作为沉积组件的示意性表示,为了简化说明,省略了许多部件,并且这些部件可以包括例如各种阀、歧管、吹扫器、加热器、容器、通风口和/或旁路。
在沉积组件300的操作期间,诸如半导体晶片(未示出)的衬底从例如衬底处理系统转移到反应室302。一旦衬底被转移到反应室302,来自气体源304-308的一种或多种气体比如前体、还原剂、载气和/或吹扫气体被引入反应室302。
上述公开的示例性实施例并不限制本发明的范围,因为这些实施例仅是本发明的实施例的示例,本发明由所附权利要求及其合法等同物限定。任何等同的实施例都在本发明的范围内。除了在此示出和描述的那些之外,本公开的各种修改比如所描述的元件的可替代有用组合对于本领域技术人员来说从描述中变得显而易见。这种修改和实施例也旨在落入所附权利要求的范围内。
Claims (21)
1.一种在衬底上沉积钒金属的方法,该方法包括:
在反应室中提供衬底;
以气相向反应室提供钒前体;以及
以气相向反应室提供还原剂,以在衬底上形成钒金属。
2.根据权利要求1所述的方法,其中,所述钒前体包括无机化合物。
3.根据权利要求1所述的方法,其中,所述钒前体包括有机化合物。
4.根据权利要求3所述的方法,其中,所述钒前体包括钒烷基酰胺基化合物或钒二烷基酰胺基化合物。
5.根据权利要求1所述的方法,其中,所述还原剂包括氢。
6.根据权利要求1所述的方法,其中,所述还原剂包括氮。
7.根据权利要求6所述的方法,其中,所述还原剂包括肼或其衍生物,或者其中,所述还原剂包括二氮烯基化合物。
8.根据权利要求6所述的方法,其中,所述还原剂包括烷基肼或二烷基肼。
9.根据权利要求1所述的方法,其中,所述还原剂包括有机金属化合物。
10.根据权利要求1所述的方法,其中,所述还原剂包括有机分子。
11.根据权利要求1所述的方法,其中,所述还原剂包括铝。
12.根据权利要求11所述的方法,其中,所述还原剂包括氢化铝(AlH3)或氢化铝的中性配体加合物。
13.根据权利要求11所述的方法,其中,所述还原剂包括含Al-H键的氨基络合物或含Al-H键的酰胺络合物。
14.根据权利要求1所述的方法,其中,沉积过程交替地和顺序地在反应室中提供钒前体和还原剂,并且在反应室中提供钒前体和还原剂之间吹扫反应室。
15.根据权利要求1所述的方法,其中,沉积过程包括热沉积过程。
16.根据权利要求1所述的方法,其中,在沉积过程中反应室内的压力小于760托,或者其中,在循环沉积过程中反应室内的压力在0.2托和760托之间。
17.一种含钒金属层,其中该层包括通过以下步骤沉积的钒金属:
在反应室中提供衬底;
以气相向反应室提供钒前体;以及
以气相向反应室提供还原剂,以在衬底上形成钒金属。
18.一种包括含钒金属层的结构,该含钒金属层通过以下步骤沉积:
在反应室中提供衬底;
以气相向反应室提供钒前体;以及
以气相向反应室提供还原剂,以在衬底上形成钒金属。
19.一种包括含钒金属层的器件,该含钒金属层通过以下步骤生产:
在反应室中提供衬底;
以气相向反应室提供钒前体;以及
以气相向反应室提供还原剂,以在衬底上形成钒金属。
20.一种用于在衬底上沉积钒金属的沉积组件,包括:
一个或多个反应室,其构造和布置成保持衬底;
前体注射器系统,其构造和布置成以气相将钒前体和/或还原剂提供到反应室中;
其中,所述沉积组件包括构造和布置成容纳和蒸发钒前体的前体容器;并且
该组件构造和布置成通过前体注射器系统向反应室提供钒前体和/或还原剂,以在衬底上沉积钒金属。
21.根据权利要求20所述的沉积组件,其中,所述沉积组件还包括容器,该容器包括构造和布置成蒸发钒前体的蒸发器。
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KR102530814B1 (ko) * | 2020-06-30 | 2023-05-10 | 주식회사 이지티엠 | 박막 증착을 위한 5족 금속 화합물 및 이를 이용한 5족 금속 함유 박막의 형성 방법 |
KR20220053482A (ko) * | 2020-10-22 | 2022-04-29 | 에이에스엠 아이피 홀딩 비.브이. | 바나듐 금속을 증착하는 방법, 구조체, 소자 및 증착 어셈블리 |
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2021
- 2021-10-18 KR KR1020210138833A patent/KR20220053482A/ko unknown
- 2021-10-18 TW TW110138466A patent/TW202217037A/zh unknown
- 2021-10-19 US US17/504,839 patent/US11873557B2/en active Active
- 2021-10-19 CN CN202111224369.7A patent/CN114381707A/zh active Pending
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US11873557B2 (en) | 2024-01-16 |
US20220127724A1 (en) | 2022-04-28 |
TW202217037A (zh) | 2022-05-01 |
KR20220053482A (ko) | 2022-04-29 |
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