CN114657530A - 过渡金属沉积方法 - Google Patents
过渡金属沉积方法 Download PDFInfo
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- CN114657530A CN114657530A CN202111549045.0A CN202111549045A CN114657530A CN 114657530 A CN114657530 A CN 114657530A CN 202111549045 A CN202111549045 A CN 202111549045A CN 114657530 A CN114657530 A CN 114657530A
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- 150000003624 transition metals Chemical class 0.000 title claims abstract description 316
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 310
- 238000000034 method Methods 0.000 title claims abstract description 92
- 238000001465 metallisation Methods 0.000 title description 3
- 239000002243 precursor Substances 0.000 claims abstract description 212
- 239000000376 reactant Substances 0.000 claims abstract description 145
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- 239000000758 substrate Substances 0.000 claims abstract description 89
- 238000000151 deposition Methods 0.000 claims abstract description 56
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- 238000005137 deposition process Methods 0.000 claims abstract description 16
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- 239000003446 ligand Substances 0.000 claims description 21
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- 239000012071 phase Substances 0.000 claims description 17
- 125000000962 organic group Chemical group 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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Images
Classifications
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
-
- 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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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/32051—Deposition of metallic or metal-silicide layers
Abstract
本公开涉及在衬底上沉积过渡金属的方法。本公开还涉及过渡金属层、包括过渡金属层的结构和器件。在该方法中,过渡金属通过循环沉积过程沉积在衬底上,并且该方法包括在反应室中提供衬底,以气相向反应室提供过渡金属前体,以及以气相向反应室提供反应物,以在衬底上形成过渡金属。过渡金属前体包括来自第4至6族中任一族的过渡金属,反应物包括选自Si,Ge或Sn的第14族元素。
Description
技术领域
本公开涉及用于制造半导体器件的方法和设备。更具体地,本公开涉及用于在衬底上沉积过渡金属的方法和系统以及包含过渡金属的层。
背景技术
半导体器件制造过程通常使用先进的沉积方法来形成具有特定性能的金属和含金属层。第4族(钛、锆、铪)、第5族(钒、铌、钽)和第6族(铬、钼和钨)中的过渡金属可具有本领域寻求的许多优点。例如,它们可用作线路后端(BEOL)或线路中端(MEOL)应用中的导体材料,或用于掩埋电源轨或用于逻辑应用中的功函数层,以及用于高级存储器应用中的字线或位线。此外,它们可用于金属栅极应用。
通过原子层沉积来沉积高质量的金属薄膜仍然具有挑战性,尤其是对于正电性元素和容易形成氮化物或碳化物相的金属。正电性元素很难还原成元素形式,通常需要强有力的还原剂、异常条件或基于等离子体的方法。一些金属元素,尤其是来自第4、5和6族的金属元素,通常从金属前体配体或沉积中用于生成金属碳化物或金属氮化物的共反应物中引入碳或氮。避免含有碳和氮的配体和共反应物是困难的,并且严重限制可能的化学物质的选择。因此,本领域需要用于沉积过渡金属或含过渡金属层的替代或改进的方法。
在本部分中阐述的任何讨论(包括问题和解决方案的讨论)已经包括在本公开中,仅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者构成现有技术。
发明内容
本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。本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。
本公开的各种实施例涉及沉积过渡金属的方法。
在本公开中,公开了通过循环沉积过程在衬底上沉积过渡金属的方法。该方法包括在反应室中提供衬底,以气相向反应室提供过渡金属前体,以及以气相向反应室提供反应物,以在衬底上形成过渡金属。根据本公开的过渡金属前体包括第4至6族中任一族的过渡金属,并且反应物包括选自Si,Ge或Sn的第14族元素。
本公开还涉及通过根据本公开的方法生产的过渡金属层。因此,在反应室中提供衬底,以气相向反应室提供包含来自第4至6族中任一族的过渡金属的过渡金属前体,并且向反应室提供包含选自Si,Ge或Sn的第14族元素的反应物,以在衬底上形成过渡金属。
在另一方面,本公开涉及一种包括通过根据本公开的方法沉积的过渡金属的结构。包含在该结构中的过渡金属可以作为层沉积。换句话说,它可以是过渡金属层。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,例如通过根据本公开的方法形成的一层或多层。该结构可以是例如BEOL中的通孔或线路,或者MEOL中的触点或局部互连。该结构也可以是栅电极中的功函数层,或逻辑应用中的掩埋电源轨,以及高级存储器应用中的字线或位线。
在又一方面,本公开涉及一种包含通过根据本公开的方法沉积的过渡金属的半导体器件。该器件可以是例如栅电极、逻辑或存储器件。
在另一方面,公开了一种沉积组件。沉积组件构造和布置成在衬底上沉积过渡金属。根据本公开的用于在衬底上沉积过渡金属的沉积组件包括一个或多个构造和布置成保持衬底的反应室,以及构造和布置成将过渡金属前体和/或反应物以气相提供到反应室中的前体注射器系统。沉积组件还包括构造和布置成包含过渡金属前体的前体容器,所述过渡金属前体包含第4至6族中任一族的过渡金属,以及构造和布置成包含反应物的反应物容器,所述反应物包含选自Si,Ge或Sn的第14族元素。沉积组件构造和布置成通过前体注射器系统向反应室提供过渡金属前体和/或反应物,以在衬底上沉积过渡金属。在根据本公开的组件中,过渡金属前体和/或反应物可以用直接液体注射器蒸发。在这样的实施例中,然后将前体和/或反应物液体从容器中泵出,并直接注入载气流中。
在本公开中应使用以下缩写:Me代表甲基(CH3),Et代表乙基(C2H5)。nPr或Pr代表正丙基,iPr代表异丙基,nBu或Bu代表正丁基,tBu代表叔丁基,sBu代表仲丁基,nPn或Pn代表正戊基,tPn代表叔戊基。Bz代表苯,Cp代表环戊二烯基。
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”、“包括”、“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
附图被包括进来以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,并且与描述一起帮助解释本公开的原理。在附图中:
图1中的图A和B示出了根据当前公开的方法的两个示例性实施例。
图2描绘了根据本公开的包括过渡金属层的示例性结构。
图3以示意方式呈现了根据本公开的沉积设备。
图4描绘了包括根据本公开沉积的过渡金属的示例性器件。
图5中的图A至D描绘了包括根据本公开沉积的过渡金属的器件。
图6是包括根据本公开沉积的过渡金属的掩埋电源轨的表示。
图7描绘了包括包含根据本公开沉积的过渡金属的功函数层的器件。
图8示出了包括根据本公开沉积的过渡金属的3D与非门中的字线。
图9显示了包括根据本公开沉积的过渡金属的DRAM中的字线的示例性实施例。
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,并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,示例性实施例或其成分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过渡金属的方法。该方法包括在反应室中提供衬底,在反应室中以气相提供过渡金属前体,以及以气相向反应室提供反应物,以在衬底上形成过渡金属。在本公开中,过渡金属可以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。元素过渡金属在这里是指氧化态为零的过渡金属。根据本公开沉积的过渡金属可以部分具有0、+2、+3、+4、+5和/或+6的氧化态。在一些实施例中,至少60%的过渡金属作为元素金属沉积。在一些实施例中,至少80%或至少90%的过渡金属作为元素金属沉积。在一些实施例中,至少93%或95%的过渡金属作为元素金属沉积。
过渡金属前体
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。然而,在某些实施例中,反应物也可以对所得化合物或元素有贡献。
如本文所用,“过渡金属前体”包括可以变成气态的气体或材料,并且可以由化学式表示,该化学式包括选自元素周期表第4族(钛、锆、铪)、第5族(钒、铌、钽)或第6族(铬、钼和钨)的过渡金属。
在一些实施例中,过渡金属前体包括第4族过渡金属。过渡金属前体因此可以包含钛(Ti)。过渡金属前体可替代地包含锆(Zr)。作为另一替代,过渡金属前体可以包括铪(Hf)。在一些实施例中,过渡金属前体中的过渡金属选自钛、锆和铪。在一些实施例中,过渡金属前体中的过渡金属选自钛和铪。
在一些实施例中,过渡金属前体包括第5族过渡金属。过渡金属前体因此可以包含钒(V),或者过渡金属前体可以包含铌(Nb),或者过渡金属前体可以包含钽(Ta)。在一些实施例中,过渡金属前体中的过渡金属选自钒、铌和钽。在一些实施例中,过渡金属前体中的过渡金属选自钒和钽。
在一些实施例中,过渡金属前体包括第6族过渡金属。过渡金属前体可以包括铬(Cr)。可替代地,过渡金属前体可以包括钼(Mo)。过渡金属前体可以包括钨(W)。在一些实施例中,过渡金属前体中的过渡金属选自铬、钼和钨。在一些实施例中,过渡金属前体中的过渡金属选自钼和钨。
在一些实施例中,过渡金属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,除过渡金属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,在组合物中提供过渡金属前体。适合用作组合物的组合物可以包括过渡金属化合物和有效量的一种或多种稳定剂。组合物可以是标准条件下的溶液或气体。
在一些实施例中,过渡金属前体包含过渡金属原子和有机配体。在一些实施例中,根据本公开,过渡金属前体包括含有过渡金属的金属-有机前体。因此,过渡金属前体是金属-有机前体。金属-有机前体在本文中是指包含金属比如根据本公开的第4-6族过渡金属以及有机配体的过渡金属前体,其中金属原子不直接键合到碳原子上。在一些实施例中,金属-有机前体包含一个过渡金属原子,其不与碳原子直接键合。在一些实施例中,金属-有机前体包含两个或更多个过渡金属原子,其中没有一个直接键合到碳原子上。在一些实施例中,金属-有机前体包含两个或更多个过渡金属原子,其中至少一个过渡金属原子不直接键合到碳原子上。
在一些实施例中,过渡金属前体包括包含根据本公开的过渡金属的有机金属化合物。因此,过渡金属前体是有机金属前体。有机金属前体在本文中是指包含过渡金属比如根据本公开的第4-6族过渡金属以及有机配体的过渡金属前体,其中金属原子不直接键合到碳原子上。在有机金属前体包含两个或更多个过渡金属原子的实施例中,所有金属原子都直接与碳原子键合。
在一些实施例中,过渡金属前体仅包括根据本公开的过渡金属原子、碳和氢。换句话说,过渡金属前体不含氧、氮或其他附加元素。然而,在一些实施例中,金属-有机或有机金属前体包括根据本公开的过渡金属、碳、氢和至少一种附加元素。附加元素可以是例如氧、氮或卤素。在一些实施例中,附加元件不直接结合到金属。因此,在一些实施例中,过渡金属前体不包含金属-氮键。在一些实施例中,过渡金属前体不包含金属-氧键。在一些实施例中,过渡金属前体不包含金属-卤素键。金属-有机或有机金属前体中的至少一种附加元素可以是配体。因此,至少一种附加元素可以是附加配体。在一些实施例中,金属-有机或有机金属前体包含附加配体,并且配体是卤化物。在一些实施例中,金属-有机或有机金属前体可以包含至少两个附加配体,并且一个或两个附加配体可以是卤化物。每个附加配体可以独立选择。卤化物可以选自氯、溴和碘。因此,配体可以是选自氯、溴和碘的卤素原子。
在一些实施例中,过渡金属前体包含至少两种有机配体。在一些实施例中,过渡金属前体包含至少三种有机配体。在一些实施例中,过渡金属前体包含四种有机配体。在一些实施例中,过渡金属前体包含有机配体和氢化物配体。在一些实施例中,过渡金属前体包含有机配体和两种或更多种氢化物配体。在一些实施例中,过渡金属前体包含两种有机配体和两种氢化物配体。在一些实施例中,一种或多种有机配体是烃配体。
在一些实施例中,过渡金属前体包括环状部分。例如,过渡金属前体可以包含苯环或环戊二烯基环。过渡金属前体可以包含一个或多个苯环。在一些实施例中,过渡金属前体包含两个苯环。一个或两个苯环可以包含烃取代基。在一些实施例中,过渡金属前体的每个苯环包含烷基取代基。烷基取代基可以是甲基、乙基或包含三个、四个、五个或六个碳原子的直链或支链烷基。例如,苯环(Bz)的烷基取代基可以是正丙基或异丙基。此外,烷基取代基可以是正、异、叔或仲形式的丁基、戊基或己基部分。在一些实施例中,过渡金属前体包括、基本由或由双(乙基苯)过渡金属构成。在一些实施例中,过渡金属前体包括、基本由或由V(Bz)2,MoBz2,CrBz2,WBz2,V(EtBz)2,Mo(EtBz)2,Cr(EtBz)2或W(EtBz)2构成。
过渡金属前体可以包含一个或多个环戊二烯基。在一些实施例中,过渡金属前体包含两个环戊二烯基。环戊二烯基可以类似地被取代为苯基。换句话说,一个或多个环戊二烯基可以包含烃取代基。在一些实施例中,环戊二烯基中的一个或两个具有烷基取代基,例如甲基、乙基或包含三个、四个、五个或六个碳原子的直链或支链烷基。例如,环戊二烯基的烷基取代基可以是正丙基、异丙基。此外,烷基取代基可以是正、异、叔或仲形式的丁基、戊基或己基部分。
根据本公开的包含环戊二烯基部分的过渡金属前体的一些示例是TiCp2Cl2,TiCp2Br2,TiCp2,TiCp2(CO)2,TiCp2I2,TiCp2H2,TiCpCl3,TiCpBr3,TiCpI3,HfCp2Cl2,HfCp2Br2,HfCp2,HfCp2(CO)2,HfCp2I2,HfCp2H2,HfCpCl3,HfCpBr3,HfCpI3,ZrCp2Cl2,ZrCp2Br2,ZrCp2,ZrCp2(CO)2,ZrCp2I2,ZrCp2H2,ZrCpCl3,ZrCpBr3,ZrCpI3,VCp2Cl2,VCp2Br2,VCp2I2,VCp2,VCp2(CO)4,TaCp2Cl2,TaCp2I2,TaCp2Br2,TaCp2H2,NbCp2,NbCp2H2,NbCp2Cl2,MoCp2Cl2,MoCp2H2,CrCp2H2,CrCp2,CrCp2Cl2,WCp2H2,WCp2Cl2,WCp2Br2和WCp2I2。
含环戊二烯基的过渡金属前体的一些另外的示例是Ti(iPrCp)2Cl2,Ti(iPrCp)2,Ti(MeCp)2Cl2,Ti(MeCp)2,Ti(EtCp)2Cl2,Ti(EtCp)2,Hf(iPrCp)2Cl2,Hf(iPrCp)2,Hf(MeCp)2Cl2,Hf(MeCp)2,Hf(EtCp)2Cl2,Hf(EtCp)2,Zr(iPrCp)2Cl2,Zr(iPrCp)2,Zr(MeCp)2Cl2,Zr(MeCp)2,Zr(EtCp)2Cl2,Zr(EtCp)2,V(iPrCp)2Cl2,V(iPrCp)2,V(MeCp)2Cl2,V(MeCp)2,V(EtCp)2Cl2,V(EtCp)2,Mo(iPrCp)2Cl2,Mo(iPrCp)2H2,Mo(EtCp)2H2,Cr(MeCp)2,Cr(EtCp)2,Cr(iPrCp)2,Cr(tBuCp)2,Cr(nBuCp)2,Cr(Me5Cp)2,Cr(Me4Cp)2,W(EtCp)2H2,W(iPrCp)2Cl2和W(iPrCp)2H2。
在一些实施例中,过渡金属前体可以包括含羰基的配体。例如,过渡金属前体可以包括、基本由或由Mo(CO)6、Mo(1,3,5-环庚三烯)(CO)3构成。此外,在一些实施例中,过渡金属前体包括含亚硝酰基的配体。例如,钼前体可以包括、基本由或由MoCp(CO)2(NO)构成。
反应物
在根据本公开的方法中,反应物包括选自硅(Si)、锗(Ge)或锡(Sn)的第14族元素。在一些实施例中,反应物包括选自Si和Ge的第14族元素。在一些实施例中,反应物包括选自Si和Sn的第14族元素。在一些实施例中,反应物包括选自Ge和Sn的第14族元素。
在一些实施例中,根据本公开,反应物包括第14族元素的一个原子。在一些实施例中,根据本公开,反应物包括第14族元素的两个原子。第14族元素的两个或更多个原子可以是相同或不同的元素。例如,反应物可以包含两个Si原子、两个Ge原子或两个Sn原子。可替代地,反应物可以包括Si原子和Ge原子、Si原子和Sn原子或Sn原子和Ge原子。在一些实施例中,反应物包括根据当前公开的相互键合的第14族元素的两个原子。
在一些实施例中,反应物包括根据当前公开的彼此键合的第14族元素的两个原子,并且第14族元素的每个原子具有附接至其的卤素原子。卤素可以是例如Cl,F或I。在一些实施例中,反应物包括根据本公开的彼此键合的第14族元素的两个原子,并且第14族元素的每个原子具有附接至其的烷基。例如,烷基可以是甲基、乙基、丙基、丁基或戊基。
在一些实施例中,反应物包括Si-Si键。在一些实施例中,反应物包括Ge-Ge键。在一些实施例中,反应物包括Sn-Sn键。在一些实施例中,反应物包括每个Si原子上附接有卤素原子的Si-Si键。在一些实施例中,反应物包括每个Ge原子上附接有卤素原子的Ge-Ge键。在一些实施例中,反应物包括每个Ge原子上附接有卤素原子的Sn-Sn键。
反应物可以包括有机基团。有机基团是包含碳氢键的基团。因此,反应物包含选自Si,Ge和Sn的第14族元素和有机基团。反应物可以包括含有至少一个碳原子的烃。反应物中可以有一个、两个、三个或四个有机基团。每个有机基团可以独立地包含1至12个碳原子。例如,每个有机基团可以独立地包括C1至C4基团(即包含1至4个碳原子)、C1至C6基团、C1至C8基团、C1-C10基团、C2至C12基团、C2至C6基团、C2至C6基团或者C4至C8基团或C4至C10基团。因此,每个有机基团可以独立地包括C1、C2、C3、C4、C5、C6、C7、C8或C10基团。有机基团可以包括烷基或芳基。有机基团可以包含一个或多个直链、支链或环状烷基。在一些实施例中,有机基团包括芳基。烷基或芳基可以被一个或多个官能团取代,例如卤素、醇、胺或苯。
例如,有机基团可以包括卤代甲烷、乙烷、丙烷、2-甲基丙烷、2,2-二甲基丙烷(新戊烷)、正丁烷、2-甲基丁烷、2,2-二甲基丁烷、正戊烷、2-甲基戊烷、3-甲基戊烷或正己烷。在一些实施例中,反应物包含两个卤素原子。在一些进一步的实施例中,反应物的至少两个卤素原子可以附接到不同的碳原子上。卤素原子可以是相同的卤素,例如溴、碘、氟或氯。可替代地,卤素可以是不同的卤素,例如碘和溴、溴和氯、氯和碘。在一些实施例中,反应物包括1,2-二卤代烷烃或1,2-二卤代烯烃或1,2-二卤代炔烃或1,2-二卤代芳烃,其中卤素附接到相邻的碳原子上。
在一些实施例中,反应物具有通式RaMXb或RcXdM-MRcXd。式中,a为0、1、2或3,b为4-a,c为0、1或2,d为3-c,R为上述有机基团,M为Si、Ge或Sn,每个X独立为任意配体。R可以是烃。如果a是两个或三个,或者c是两个,则独立选择每个R。在一些实施例中,每个R选自烷基和芳基。在一些实施例中,R是如上所述的有机基团。在一些实施例中,R是烷基或芳基。为了清楚起见,X可以代表一种反应物物种中的不同配体。因此,在一些实施例中,反应物可以是例如SiH2Br2,SiH2I2或SiH2Cl2。
在一些实施例中,反应物具有更具体的分子式RaSiXb。更具体地,反应物可以具有式R3SiX,R2SiX2,RSiX3或SiX4。然而,在一些实施例中,硅原子不包含四个相同的取代基。在一些实施例中,反应物不是SiH4。在一些实施例中,反应物不是SiH2Me2。在一些实施例中,反应物不是SiH2Et2。在一些实施例中,反应物不是Si2H2。
在一些实施例中,反应物具有更具体的分子式RaGeXb。更具体地,反应物可以具有式R3GeX,R2GeX2,RGeX3或GeX4。然而,在一些实施例中,Ge原子不包含四个相同的取代基。在一些实施例中,反应物不是GeH4。
在一些实施例中,反应物具有更具体的分子式RaSnXb。更具体地,反应物可以具有式R3SnX,R2SnX2,RSnX3或SnX4。然而,在一些实施例中,锡原子不包含四个相同的取代基。在一些实施例中,反应物不是SnH4。
在一些实施例中,X是氢、取代或未取代的烷基或芳基或卤素。在一些实施例中,X是H。在一些实施例中,X是烷基或芳基。在一些实施例中,X是C1至C4烷基。在一些实施例中,X是取代的烷基或芳基。在一些实施例中,X是取代的烷基或芳基,其中取代基与M相同。在一些实施例中,X选自H,Me,Et,nPr,iPr,nBu,tBu,M’Me3,M’Et3,M’Pr3,M’Bu3,Cl,Br或I,其中M’与M相同。因此,在这种实施例中,对于式RaSiXb的反应物,M’是Si,对于式RaGeXb的反应物,M’是Ge,对于式RaSnXb的反应物,M是Sn。
在一些实施例中,过渡金属作为层沉积在衬底上。在这样的实施例中,过渡金属形成过渡金属层。如本文所用,“过渡金属层”可以是包含过渡金属的材料层。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,例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、纳米颗粒或者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。
在不将本公开限制于任何特定理论的情况下,在一些实施例中,可能产生具有低电阻率的过渡金属层。根据本公开的过渡金属层的电阻率可以为约5μΩcm到约300μΩcm,或约5μΩcm到约100μΩcm,或约5μΩcm到约50μΩcm,例如约10μΩcm、15μΩcm、20μΩcm或30μΩcm。在其他实施例中,过渡金属层的电阻率可以是约50μΩcm、100μΩcm、150μΩcm或200μΩcm。
过渡金属可以至少部分是元素形式。因此,过渡金属的氧化态可以为零。过渡金属层可以包括附加元素,例如氮、碳和/或氧。其他附加或替代元素也是可能的。在一些实施例中,过渡金属层可以包括显著比例的过渡金属以外的其他元素。然而,在一些实施例中,过渡金属层可以基本仅包含过渡金属。因此,过渡金属层可以包括、基本由或由过渡金属构成。在一些实施例中,过渡金属层可以是种子层。种子层可用于增强另一层的沉积。
在一些实施例中,过渡金属层可以包括例如约60至约99原子百分比(原子%)过渡金属,或约75至约99原子%过渡金属,或约75至约95原子%过渡金属,或约75至约89原子%过渡金属。通过根据本公开的方法沉积的过渡金属层可以包括例如约80原子%,约83原子%,约85原子%,约87原子%,约90原子%,约95原子%,约97原子%或约99原子%过渡金属。在一些实施例中,过渡金属层可以基本由或由过渡金属构成。在一些实施例中,过渡金属层可以基本由或由过渡金属构成。由过渡金属构成的层可以包括可接受量的杂质,例如氧、碳、氯或其他卤素,和/或氢,其可以来源于用于沉积过渡金属层的一种或多种前体。
在一些实施例中,过渡金属层可以包括小于约30原子%,小于约20原子%,小于约10原子%,小于约8原子%,小于约7原子%,小于约5原子%,或小于约2原子%氧。在一些实施例中,过渡金属层可以包括少于约20原子%,小于约15原子%,小于约10原子%,小于约8原子%,小于约6原子%,小于约5原子%,小于4.5原子%,或小于约3原子%碳。
衬底可以是可用于形成或在其上形成结构、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,例如硅(例如单晶硅)、其他第四族材料,例如锗,或者其他半导体材料,例如第二-六族或者第三-五族半导体材料,并且可以包括在块体材料之上或者之下的一层或多层。此外,衬底可以包括各种特征,例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至少一部分块体半导体材料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,例如钨、钌、钼、钴、铝或铜,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。
根据本公开的沉积过渡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。
在根据本公开的方法中,当过渡金属前体在反应室中时,它可以处于气相。过渡金属前体在被提供到反应室之前的某些时间点可以是部分气态或液态,或者甚至是固态。换句话说,过渡金属前体可以是固体、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纳部中。当执行输送到反应室中时,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者它们的任意组合。因此,根据本公开的方法可以包括在将过渡金属前体提供给反应室之前加热过渡金属前体。在一些实施例中,在容器中将过渡金属前体加热到至少60℃,或至少100℃,或至少110℃,或至少120℃,或至少130℃,或至少140℃。在一些实施例中,过渡金属前体被加热到至多160℃,或至多140℃,或至多120℃,或至多100℃,或至多80℃,或至多60℃。注射器系统也可被加热以改善过渡金属前体向反应室的气相输送。
在本公开中,“气体”可以包括在常温常压(NTP)下为气体的材料、蒸发的固体和/或蒸发的液体,并且可以由单一气体或气体混合物构成,这取决于情况。过渡金属前体可以气相形式提供给反应室。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。除了处理气体之外的气体即不经过前体注射器系统、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。
在根据本公开的方法中,反应物可以与包含化学吸附的过渡金属前体的衬底接触。过渡金属前体向过渡金属的转化可以发生在衬底表面。在一些实施例中,转化可以至少部分在气相中进行。
在当前公开中,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(VCD)过程。术语“循环沉积过程”可以指将前体和/或反应物顺序引入反应室,以在衬底上沉积材料,例如过渡金属。循环沉积包括诸如原子层沉积(ALD)、循环化学气相沉积(循环VCD)和包括ALD成分和循环VCD成分的混合循环沉积过程的处理技术。该过程可以包括在反应室中提供前体之间或提供前体和反应物之间的吹扫步骤。
该过程可以包括一个或多个循环阶段。例如,过渡金属和反应物的脉冲可以重复。在一些实施例中,该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,反应物可以连续地提供在反应室中。在这样的实施例中,该过程包括反应物的连续流动。
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。这里使用的术语原子层沉积也意味着包括当用前体/反应物和可选的吹扫气体的交替脉冲执行时由相关术语指定的过程,例如化学气相原子层沉积。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),形成不容易与附加前体反应(即自限制反应)的材料的单层或亚单层。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。
CVD型过程通常涉及两种或更多种反应物之间的气相反应。前体和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,提供前体和反应物,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,过渡金属前体、反应物或两者以脉冲提供给反应室。在一些实施例中,过渡金属前体以脉冲供应,反应物以脉冲供应,并且在过渡金属前体和反应物的连续脉冲之间吹扫反应室。将反应物或过渡金属前体提供到反应室中的持续时间(即反应物或过渡金属前体脉冲时间)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1秒至约20秒,或约0.5秒至约10秒,或约5秒至约15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。过渡金属前体或反应物脉冲的持续时间可以是例如0.03秒、0.1秒、0.5秒、1秒、1.5秒、2秒、2.5秒、3秒、4秒、5秒、8秒、10秒、12秒、15秒、25秒、30秒、40秒、50秒或60秒。在一些实施例中,过渡金属前体脉冲时间可以是至少5秒,或至少10秒,或至少20秒,或至少30秒。在一些实施例中,过渡金属前体脉冲时间可以是至多5秒,或至多10秒,或至多20秒,或至多30秒。在一些实施例中,反应物脉冲时间可以是至少15秒,或至少30秒,或至少45秒,或至少60秒。在一些实施例中,反应物脉冲时间可以是至多15秒,或至多30秒,或至多45秒,或至多60秒。
过渡金属前体和反应物的脉冲时间根据所讨论的过程而独立变化。合适的脉冲时间的选择可以取决于衬底拓扑。对于更高纵横比的结构,可能需要更长的脉冲时间来在高纵横比结构的不同区域获得足够的表面饱和度。此外,所选择的过渡金属前体和反应物化学物质可以影响合适的脉冲时间。出于过程优化的目的,只要能够获得合适的层特性,较短的脉冲时间可能是优选的。在一些实施例中,过渡金属前体脉冲时间比反应物脉冲时间长。在一些实施例中,反应物脉冲时间比过渡金属前体脉冲时间长。在一些实施例中,过渡金属前体脉冲时间与反应物脉冲时间相同。
在一些实施例中,向反应室提供反应物或过渡金属前体包括在衬底上脉冲反应物或过渡金属前体。在某些实施例中,几分钟范围内的脉冲时间可用于过渡金属前体和/或反应物。在一些实施例中,在反应物被脉冲到反应室之前,过渡金属前体可被脉冲不止一次,例如两次、三次或四次。类似地,在过渡金属前体被脉冲(即提供)到反应室之前,反应物可以有多于一个脉冲,例如两个、三个或四个脉冲。
过渡金属前体或反应物的流量(即分别过渡金属前体或反应物流量)可以从约5sccm变化到约20slm。在向反应室提供过渡金属前体或反应物的过程中,过渡金属前体或反应物的流量可以小于3000sccm,或小于2000sccm,或小于1000sccm,或小于500sccm,或小于100sccm。过渡金属前体或反应物流量可以是例如从500sccm到1200sccm,例如600sccm、800sccm或1000sccm。在一些实施例中,过渡金属前体或反应物到反应室的流量在50sccm和3000sccm之间,或在50sccm和2000sccm之间,或在50sccm和1000sccm之间。在一些实施例中,过渡金属前体或反应物到反应室的流量在50sccm和900sccm之间,或在50sccm和800sccm之间,或在50sccm和500sccm之间。在一些实施例中,可以使用更高的流量。例如,过渡金属前体或反应物流量可以是5slm或更高。在一些实施例中,过渡金属前体或反应物流量可以是10slm、12slm或15slm或20slm。
在一些实施例中,该方法包括在反应室中提供反应物之前,通过惰性气体从反应室中去除过量的过渡金属前体。在一些实施例中,在反应室中提供过渡金属前体和在反应室中提供反应物之间吹扫反应室。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过渡金属前体或反应物的两个脉冲之间被吹扫。
如本文所用,术语“吹扫”可以指这样的过程,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的气体比如氩或氮替换反应室内的气体,从衬底表面去除气相前体和/或气相副产物。吹扫可以在两个相互反应的气体脉冲之间进行。然而,吹扫可以在两个彼此不反应的气体脉冲之间进行。例如,可以在两种前体的脉冲之间或前体和反应物之间提供吹扫。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,吹扫可以在时间或空间上或者在两者上进行。例如,在暂时吹扫的情况下,吹扫步骤可用于例如向反应器室提供第一前体、向反应器室提供吹扫气体和向反应器室提供第二前体的时间顺序,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0.01秒至约20秒、约0.05秒至约20秒、或约1秒至约20秒、或约0.5秒至约10秒、或约1秒至约7秒,例如5秒、6秒或8秒。然而,如果需要,也可以使用其它吹扫时间,例如在需要在极高纵横比结构或具有复杂表面形态的其它结构上高度共形台阶覆盖的地方,或者可以用于特定的反应器类型,例如分批反应器。
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,温度升高提供了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过渡金属所需的能量。在一些实施例中,根据当前公开的方法是等离子体增强沉积方法,例如PEALD或PECVD。
在一些实施例中,过渡金属可以在约20℃至约800℃的温度下沉积。例如,过渡金属可以在约20℃至约450℃或约50℃至约450℃或约150℃至约450℃或约450℃至约800℃的温度下沉积。在本公开的一些实施例中,过渡金属可以在约20℃至约300℃或约300℃至约600℃的温度下沉积。在一些实施例中,过渡金属可以在约50℃至约150℃或约250℃至约400℃或约500℃至约700℃的温度下沉积。例如,过渡金属可以在约75℃或约125℃或约175℃或约225℃或约200℃或约325℃或约375℃或约550℃或约650℃或约750℃的温度下沉积。
可以为不同的过程步骤独立选择反应室中的压力。在一些实施例中,在过渡金属前体脉冲期间可以使用第一压力,在反应物脉冲期间可以使用第二压力。在吹扫或其他过程步骤期间,可以使用第三或另外的压力。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0.1托和760托之间,或在1托和100托之间,或在1托和10托之间。在一些实施例中,沉积过程中反应室内的压力小于约0.001托、小于0.01托、小于0.1托、小于1托、小于10托、小于50托、小于100托或小于300托。在一些实施例中,在根据本公开的方法的至少一部分期间,反应室内的压力小于约0.001托、小于0.01托、小于0.1托、小于1托、小于10托或小于50托、小于100托或小于300托。例如,在一些实施例中,第一压力可以是约0.1托、约0.5托、约1托、约5托、约10托、约20托或约50托。在一些实施例中,第二压力为约0.1托、约0.5托、约1托、约5托、约10托、约20托或约50托。
通过附图中描绘的以下示例性实施例进一步解释本公开。这里呈现的图示不意味着是任何特定材料、结构或器件的实际视图,而仅仅是描述当前公开的实施例的示意性表示。应当理解,附图中的元件是为了简单和清楚而示出的,并不一定是按比例绘制的。例如,图中一些元件的尺寸可能相对于其他元件被放大,以帮助提高对本公开的所示实施例的理解。附图中描绘的结构和器件可以包含附加的元件和细节,为了清楚起见,可以将其省略。
图1中的图A和B示出了根据当前公开的方法100的示例性实施例。方法100可用于形成包含过渡金属的层,即过渡金属层。过渡金属层可以在结构或器件的形成过程中使用,例如这里描述的结构或器件。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执行,但该结构或器件的其他、之前或之后的制造步骤在同一组合工具的附加反应室中执行。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,衬底可被带到期望的温度和压力,用于在反应室中提供过渡金属前体104和/或在反应室中提供反应物106。反应室内的温度(例如衬底或衬底支撑件的温度)可以是例如约50℃至约350℃,约150℃至约400℃,约200℃至约350℃或约500℃至约750℃。作为另一示例,反应室内的温度可以是约275℃至约325℃,或约450℃至约600℃。反应室内的示例性温度可以是100℃、250℃、300℃、550℃、650℃或700℃。
反应室内的压力可以小于760托,例如400托、100托、50托或20托、5托、托或0.1托。不同的压力可用于不同的过程步骤。
过渡金属前体被提供在包含衬底104的反应室中。在不将当前公开限制于任何特定理论的情况下,在反应室中提供过渡金属前体期间,过渡金属前体可以化学吸附在衬底上。在反应室中提供过渡金属前体的持续时间(过渡金属前体脉冲时间)可以是例如0.01秒、0.5秒、1秒、1.5秒、2秒、4秒、10秒、20秒、35秒、50秒或60秒。在一些实施例中,在反应室中提供过渡金属前体的持续时间(过渡金属前体脉冲时间)可以长于5秒或长于10秒或长于30秒。可替代地,过渡金属吹扫时间可以短于60秒、短于30秒、短于10秒、短于4秒、短于1秒或短于0.5秒。
当反应物被提供在反应室中106时,它可以与化学吸附的过渡金属前体或其衍生物种反应,以形成过渡金属。在反应室中提供反应物的持续时间(反应物脉冲时间)可以是例如0.01秒、0.2秒、0.5秒、1秒、3秒、4秒、5秒、7秒、10秒、11秒、15秒、25秒、30秒、45秒或60秒。在一些实施例中,在反应室中提供反应物的持续时间可以短于60秒、短于40秒、短于20秒、短于10秒、短于4秒或约3秒。相反,在一些实施例中,可以定义反应物脉冲的最小持续时间。例如,反应物脉冲时间可以短于60秒、短于40秒、短于25秒、短于15秒、短于8秒、短于5秒或短于2秒。
在一些实施例中,过渡金属前体可以在提供给反应室之前被加热。在一些实施例中,反应物可以在提供给反应室之前被加热。在一些实施例中,反应物可以在提供给反应室之前保持在环境温度下。
以任何顺序执行的阶段104和106可以形成沉积循环,导致过渡金属的沉积。在一些实施例中,可以重复(回路108)过渡金属沉积的两个阶段,即在反应室中提供过渡金属前体和反应物(104和106)。这样的实施例包含多个沉积循环。沉积的过渡金属的厚度可以通过调节沉积循环的次数来调节。沉积循环(回路108)可以重复,直到获得期望的过渡金属厚度。例如,可以执行约50、100、200、300、400、500、700、800、1000、1200、1500或2000个沉积循环。
在一个循环期间沉积的过渡金属量(每个循环的生长)根据处理条件而变化,并且可以是例如约/循环到约/循环,或约/循环到约/循环,/循环到约/循环,例如约/循环到约/循环或约/循环到约/循环。例如,生长速率可能为约/循环、/循环、/循环、/循环、/循环、/循环、/循环、/循环。在一些实施例中,过渡金属层的生长速率可以更低,例如约/循环到约/循环,或约/循环到约/循环,而在一些其他实施例中,生长速率可以更高,例如约/循环到约/循环,约/循环到约/循环,或约/循环到约/循环。取决于沉积条件、沉积循环数等,可以沉积不同厚度的过渡金属层。例如,过渡金属或含过渡金属的层的厚度可以为约0.2nm至60nm、或约1nm至50nm、或约0.5nm至25nm、或约1nm至50nm、或约10nm至60nm。过渡金属层的厚度可以例如为约0.2nm、0.3nm、0.5nm、1nm、1.5nm、2nm、2.5nm、3nm、3.5nm、4nm、4.5nm、5nm、6nm、8nm、10nm、15nm、20nm、25nm、30nm、35nm、40nm、50nm、70nm、85nm或100nm。可以根据所讨论的应用来选择期望的厚度。
过渡金属前体和反应物可以在独立的步骤(104和106)中提供在反应室中。图1B示出了根据当前公开的实施例,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/或反应物可以通过惰性气体比如氩(Ar)、氮(N2)或氦(He)和/或真空压力暂时彼此分离。过渡金属前体和反应物的分离可替代地是空间的。
吹扫反应室103、105可以防止或减轻过渡金属前体和反应物之间的气相反应,并能够实现可能的自饱和表面反应。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过渡金属前体和反应物。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种不会冷凝成单层或多层,也不会在表面上热分解。
当执行方法100时,过渡金属沉积到衬底上。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,导致化学气相沉积过程的某些部分,但仍利用过渡金属前体和反应物的顺序引入。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一段时间的重叠,导致沉积的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反应物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。
在一些实施例中,过渡金属前体与衬底表面接触104,过量的过渡金属前体被惰性气体或真空部分或基本完全去除105,反应物与包含过渡金属前体的衬底表面接触。过渡金属前体可以一个或多个脉冲与衬底表面接触104。换句话说,过渡金属前体104的脉冲可以重复。衬底表面上的过渡金属前体可以与反应物反应,以在衬底表面上形成过渡金属。反应物的脉冲106也可以重复。在一些实施例中,可以首先在反应室中提供反应物106。此后,可以一个或多个脉冲104吹扫105反应室和在反应室中提供的过渡金属前体。
在一些实施例中,根据本公开的过渡金属层的电阻率可以为约5μΩcm到约300μΩcm。例如,根据本公开的过渡金属层的电阻率可以是10μΩcm、15μΩcm、20μΩcm、50μΩcm、100μΩcm、150μΩcm或200μΩcm。具有所述电阻率的层的厚度可以是例如10nm、20nm、30nm、40nm、50nm或60nm。
在一些实施例中,沉积的过渡金属层的厚度不均匀性小于约3%。
过渡金属层的电阻率可以通过使用沉积后退火来降低。退火可以在沉积过渡金属层之后直接进行,即不沉积附加层。可替代地,退火可以在附加层已经沉积之后进行。可以在退火之前覆盖过渡金属层。覆盖层可以包括、基本由或由氮化硅构成。可以使用约320℃到约500℃的退火温度。例如,退火温度可以是330℃、350℃、380℃、400℃、430℃或450℃或470℃。退火可以在包括、基本由或由氩、氩氢混合物、氢、氮或氮氢混合物构成的气体气氛中进行。退火的持续时间可以是约1分钟至约60分钟,例如5分钟、20分钟、30分钟或45分钟。退火可以在0.05至760托的压力下进行。例如,退火期间的压力可以是约1托、约10托、约100托或约500托。
在非限制性示例中,过渡金属例如钼层可以在至少5托的压力下沉积,例如在约6托、7托或8托的压力下沉积。使用5托至10托之间的压力可以导致过渡金属的有利生长速率。在一些实施例中,过渡金属的生长速率可以是例如约/循环或约/循环。相对于低压沉积(即沉积压力低于3托),5托至10托之间的压力可以将沉积材料的厚度不均匀性降低例如约60%至90%。此外,可以减少过渡金属层生长开始之前的培养时间。在示例性实施例中,过渡金属前体是Mo(EtBz)2,反应物包括二卤代烷,比如二碘乙烷。
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、过渡金属层204和在衬底202和过渡金属层204之间(例如与一个或两者接触)的可选底层206。衬底202可以是或包括这里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。可替代地,衬底材料可以包括金属。
过渡金属层204可以根据这里描述的方法形成。在形成底层206的实施例中,底层206可以使用循环沉积过程形成。在一些实施例中,过渡金属层204可以主要包括比如至少50原子%,至少70原子%,至少90原子%或至少95原子%元素过渡金属。在一些实施例中,过渡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。作为进一步的替代,根据本公开的结构或器件可以在衬底和过渡金属层之间包括多于一层。
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、过渡金属前体容器304、反应物容器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,比如ALD或CVD反应室。
过渡金属前体容器304可以包括容器和一种或多种本文所述的过渡金属前体—单独或与一种或多种载气(例如惰性气体)混合。反应物容器306可以包括容器和本文所述的一种或多种反应物—单独或与一种或多种载气混合。吹扫气体源308可以包括一种或多种如本文所述的惰性气体。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。在一些实施例中,可以加热前体容器中的过渡金属前体。在一些实施例中,加热容器,使得过渡金属前体达到约30℃至约160℃之间的温度,比如约100℃至约145℃,例如85℃、100℃、110℃、120℃、130℃或140℃。
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各自的源304-308引入前体、反应物和吹扫气体。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的适当操作。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、反应物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反应物源以及吹扫气体源。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、净化器、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、反应物、载气和/或吹扫气体被引入反应室302。
图4示出了半导体器件400中的线路406和通孔404。该器件位于半导体衬底402上。衬底402可以包含本公开中描述的任何衬底材料。附加函数层(图中未示出)可以存在于衬底402上。通孔404与衬底和线路406接触。通孔404可以包括、基本由或由根据本公开沉积的过渡金属构成。线路406可以包括、基本由或由根据本公开沉积的过渡金属构成,或者它可以包括、基本由或由另一种金属比如铜构成。通孔404和线路406被低k材料包围。
图5中的图A至D举例说明了根据本发明在不同接触应用中沉积的过渡金属。在所有图中,衬底用数字502表示,源极用数字504表示,漏极用数字506表示,栅极用数字508表示,接触用数字512表示。在图A中,根据本公开沉积的过渡金属用于源极接触510和漏极接触514。在图B中,根据本公开沉积的过渡金属用于栅极接触510,在图C中,用于栅极508和源极504之间的局部互连510。在图D中,过渡金属用于通孔和接触512之间的连接510。在所有描述的示例中,使用根据本公开的过渡金属的结构可以包括、基本由或由所述过渡金属构成。
图6描绘了包括根据本公开沉积的过渡金属的掩埋电源轨602和FinFET结构604。
图7示出了栅极702,其中功函数层704包括、基本由或由根据本发明沉积在如图5所示的类似器件中的过渡金属构成。
图8是3D与非门800的图示,其中字线804包括、基本由或由根据当前公开沉积的过渡金属构成。该图显示了作为参考的沟道806、隧道氧化物808、电荷俘获层810和阻挡氧化物812的示例性实施例。
图9示出了具有掩埋字线906的DRAM900的示例性实施例。在图中,902表示源极,904表示栅极,910表示位线。掩埋字线906包括、基本由或由根据本公开沉积的过渡金属构成。
上述公开的示例性实施例并不限制本发明的范围,因为这些实施例仅仅是本发明的实施例的示例,本发明的范围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)
1.一种通过循环沉积过程在衬底上沉积来自第4至6族中任一族的过渡金属的方法,该方法包括:
在反应室中提供衬底;
以气相向反应室提供过渡金属前体;以及
以气相向反应室提供反应物,以在衬底上形成过渡金属;其中,
过渡金属前体包括来自第4至6族中任一族的过渡金属,反应物包括选自Si,Ge或Sn的第14族元素。
2.根据权利要求1所述的方法,其中,所述过渡金属前体包括第6族过渡金属。
3.根据权利要求2所述的方法,其中,是第6族过渡金属是钼或钨。
4.根据权利要求2所述的方法,其中,所述第6族过渡金属是钼。
5.根据权利要求1所述的方法,其中,所述过渡金属前体包括金属-有机前体或有机金属前体。
6.根据权利要求5所述的方法,其中,所述过渡金属前体包括附加配体。
7.根据权利要求6所述的方法,其中,所述附加配体是卤化物。
8.根据权利要求5所述的方法,其中,所述过渡金属前体包括苯或环戊二烯基。
9.根据权利要求1所述的方法,其中,所述反应物包括有机基团。
10.根据权利要求1所述的方法,其中,所述反应物具有通式RaMXb或RcXdM-MRcXd,其中a是0-3,b是4-a,c是0、1或2,d是3-c,R是烃,M是Si,Ge或Sn,并且每个X独立地是任何配体。
11.根据权利要求10所述的方法,其中,R是烷基或芳基。
12.根据权利要求10所述的方法,其中,X是氢、取代或未取代的烷基或芳基或卤素。
13.根据权利要求12所述的方法,其中,X是取代的烷基或芳基,并且其中取代基与M相同。
14.根据权利要求1所述的方法,其中,所述过渡金属前体以脉冲供应,反应物以脉冲供应,并且在过渡金属前体和反应物的连续脉冲之间吹扫反应室。
15.根据权利要求1所述的方法,其中,所述反应室中的压力在0.1至100托之间。
16.根据权利要求1所述的方法,其中,所述循环沉积过程包括热沉积过程。
17.根据权利要求1所述的方法,其中,所述衬底包括介电表面,并且过渡金属沉积在介电表面上。
18.根据权利要求1所述的方法,其中,过渡金属作为层沉积在衬底上。
19.一种通过循环沉积过程生产的过渡金属层,该循环沉积过程包括:
在反应室中提供衬底;
以气相向反应室提供过渡金属前体;以及
以气相向反应室提供反应物,以在衬底上形成过渡金属;其中,
过渡金属前体包括来自第4至6族中任一族的过渡金属,反应物包括选自Si,Ge或Sn的第14族元素。
20.根据权利要求19所述的层,具有约15μΩcm至约300μΩcm的电阻率,比如20μΩcm、50μΩcm、100μΩcm、150μΩcm或200μΩcm。
21.一种用于在衬底上沉积过渡金属的沉积组件,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过渡金属前体和/或反应物提供到反应室中;
其中,所述沉积组件包括前体容器,其构造和布置成包含过渡金属前体,所述过渡金属前体包括来自第4至6族中任一族的过渡金属;以及
反应物容器,其构造和布置成包含包括选自Si,Ge或Sn的第14族元素;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过渡金属前体和/或反应物,以在衬底上沉积过渡金属。
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KR20210130646A (ko) | 2020-04-21 | 2021-11-01 | 에이에스엠 아이피 홀딩 비.브이. | 기판을 처리하기 위한 방법 |
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2021
- 2021-12-15 TW TW110146852A patent/TW202231903A/zh unknown
- 2021-12-16 KR KR1020210180973A patent/KR20220090438A/ko unknown
- 2021-12-17 CN CN202111549045.0A patent/CN114657530A/zh active Pending
- 2021-12-17 US US17/554,009 patent/US11885020B2/en active Active
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US11885020B2 (en) | 2024-01-30 |
US20220195599A1 (en) | 2022-06-23 |
KR20220090438A (ko) | 2022-06-29 |
TW202231903A (zh) | 2022-08-16 |
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