CN112805818A - 用低电阻率金属填充半导体器件中的凹陷特征的方法 - Google Patents
用低电阻率金属填充半导体器件中的凹陷特征的方法 Download PDFInfo
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- CN112805818A CN112805818A CN201980066266.7A CN201980066266A CN112805818A CN 112805818 A CN112805818 A CN 112805818A CN 201980066266 A CN201980066266 A CN 201980066266A CN 112805818 A CN112805818 A CN 112805818A
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Abstract
披露了一种用低电阻率金属填充凹陷特征的方法。该方法包括:提供图案化衬底,该图案化衬底包含形成在第一层中的凹陷特征和暴露在该凹陷特征中的第二层;并且用表面改性剂预处理该衬底,该表面改性剂增大在该第二层上相对于在该第一层上的金属沉积选择性;通过气相沉积将金属层沉积在该衬底上,其中该金属层优先地沉积在该凹陷特征中的第二层上;以及移除沉积在该第一层上、包括沉积在场区域上和该第一层的位于该凹陷特征中的侧壁上的金属核,以在该凹陷特征中的第二层上选择性地形成该金属层。该预处理、沉积和移除的步骤可以重复至少一次以增加该金属层在该凹陷特征中的厚度。
Description
相关申请的交叉引用
本申请涉及并要求2018年10月10日提交的美国临时专利申请序列号62/744,038的优先权,该美国临时专利申请的全部内容通过引用并入本文。
技术领域
本发明涉及半导体处理和半导体器件,并且更具体地,涉及一种用低电阻率金属填充半导体器件中的凹陷特征的方法。
背景技术
半导体器件含有被填充的凹陷特征,比如形成在比如层间电介质(ILD)的介电材料中的沟槽或过孔。由于在凹陷特征底部的金属层上相对于在介电材料上的有限金属沉积选择性,凹陷特征的选择性金属填充是有问题的。这使得在凹陷特征周围的场区域(水平区域)上和凹陷特征的侧壁上开始不想要的金属核沉积之前,难以在自底向上的沉积过程中用金属充分填充凹陷特征。
发明内容
本发明的实施例描述了一种用低电阻率金属填充半导体器件中的凹陷特征的方法。根据一个实施例,该方法包括:提供图案化衬底,该图案化衬底包含形成在第一层中的凹陷特征和暴露在该凹陷特征中的第二层;和用表面改性剂预处理该衬底,该表面改性剂相对于在该第一层上的金属沉积选择性增大在该第二层上的金属沉积选择性。该方法进一步包括:通过气相沉积将金属层沉积在该衬底上,其中该金属层优先地沉积在该凹陷特征中的第二层上;以及移除沉积在该第一层上、包括沉积在场区域上和该第一层的位于该凹陷特征中的侧壁上的金属核,以在该凹陷特征中的第二层上选择性地形成该金属层。该预处理、沉积和移除的步骤可以重复至少一次以增加该金属层在该凹陷特征中的厚度。
根据另一实施例,该方法包括:提供图案化衬底,该图案化衬底包含形成在第一层中的凹陷特征和暴露在该凹陷特征中的第二层;将含金属层沉积在该衬底上,包括沉积在该凹陷特征中;从该凹陷特征的底部并从围绕该凹陷特征的场区域各向异性地移除该含金属层,以在该凹陷特征的侧壁上形成该含金属层。该方法进一步包括:用表面改性剂预处理该衬底,该表面改性剂相对于在该第一层上的金属沉积选择性增大在该凹陷特征的侧壁上和在该第二层上的含金属层上金属沉积选择性;通过气相沉积将金属层沉积在该衬底上,其中该金属层相对于在围绕该凹陷特征的场区域上优先地沉积在这些侧壁上和该凹陷特征中的第二层上的含金属层上;以及移除沉积在该场区域上的金属核,以在该凹陷特征中选择性地形成该金属层。该预处理、沉积和移除的步骤可以重复至少一次以增加该金属层在该凹陷特征中的厚度。
根据另一实施例,该方法包括:提供包含形成在材料中的凹陷特征的图案化衬底;将金属氮化物层沉积在该衬底上,包括沉积在该凹陷特征中和围绕该凹陷特征的场区域上;氧化该场区域上的金属氮化物层。该方法进一步包括:通过气相沉积将金属层沉积在该衬底上,其中该金属层优先地沉积在该凹陷特征中未被氧化的该金属氮化物层上;以及移除沉积在该场区域上的金属核,以在该凹陷特征中选择性地形成该金属层。该沉积和移除的步骤可以重复至少一次以增加该金属层在该凹陷特征中的厚度。
根据另一实施例,该方法包括:提供包含形成在材料中的凹陷特征的图案化衬底;将金属氧化物层沉积在该衬底上,包括沉积在该凹陷特征中和围绕该凹陷特征的场区域上;氮化该场区域上和该凹陷特征中的金属氧化物层;氧化该场区域上的氮化的金属氧化物层。该方法进一步包括:通过气相沉积将金属层沉积在该衬底上,其中该金属层优先地沉积在该凹陷特征中未被氧化的氮化的该金属氧化物层上;以及移除沉积在该场区域上的金属核,以在该凹陷特征中选择性地形成该金属层。该沉积和移除的步骤可以重复至少一次以增加该金属层在该凹陷特征中的厚度。
根据另一实施例,该方法包括:提供包含形成在材料中的凹陷特征的图案化衬底;将金属氧化物层沉积在该衬底上,包括沉积在该凹陷特征中和围绕该凹陷特征的场区域上;和氮化该场区域上的金属氧化物层。该方法进一步包括:通过气相沉积将金属层沉积在该衬底上,其中该金属层优先地沉积在该场区域上的氮化的金属氧化物层上;以及移除沉积在该凹陷特征中的金属核,以在该场区域上选择性地形成该金属层。该沉积和移除的步骤可以重复至少一次以增加该金属层在该凹陷特征中的厚度。
附图说明
通过参考以下在结合附图考虑时的具体实施方式,由于本发明变得更好理解而将容易获得对本发明及其许多附带优点的更完整的理解,其中:
图1A至图1F示意性地示出了根据本发明的实施例的用于在凹陷特征中进行选择性金属形成的方法;
图2A至图2E示意性地示出了根据本发明另一实施例的用于在凹陷特征中进行选择性金属形成的方法;
图3A至图3E示意性地示出了根据本发明另一实施例的用于在凹陷特征中进行选择性金属形成的方法;
图4A至图4F示意性地示出了根据本发明另一实施例的用于在凹陷特征中进行选择性金属形成的方法;
图5A至图5E示意性地示出了根据本发明另一实施例的用于在凹陷特征中进行选择性金属形成的方法;
图6A至图6D示意性地示出了根据本发明另一实施例的用于在凹陷特征中进行选择性金属形成的方法;以及
图7示出了在图案化衬底上的凹陷特征中具有选择性Ru金属形成的SEM图像。
具体实施方式
本发明的实施例提供了用于在半导体器件的凹陷特征中选择性地形成低电阻率金属的方法。该方法可以用于用低电阻率金属完全填充凹陷特征。根据一个实施例,通过气相沉积,金属沉积选择性按以下顺序增大:含Si材料<含金属层<金属。例如,沉积的金属可以包括Ru金属、Co金属或W金属。金属沉积的孵化时间针对金属最短并且针对含Si材料最长。孵化时间是指沉积过程期间直到在表面上开始金属沉积为止的延迟。在一个实施例中,这可以用于指相对于在凹陷特征上方的表面优先地在凹陷特征中形成金属。含Si材料可以包括SiO2、SiON或SiN。SiO2可以沉积为层或通过Si的氧化(例如通过暴露于空气、氧(O2或O)、臭氧或H2O)而形成。SiN可以沉积为层或通过Si的氮化(例如通过暴露于N或NH3)而形成。SiON可以沉积为层或通过氮化SiO2、通过SiN的氧化、或通过Si的氧化和氮化而形成。含金属层可以包括金属氧化物、金属氮化物、金属碳化物、金属硅化物、金属硫化物或金属磷化物。金属硅化物可以通过金属沉积在Si上或Si沉积在金属上、然后通过热处理、或通过在沉积过程期间形成金属硅化物而形成。金属可以例如包括Ru金属、Co金属或W金属。
图1A至图1F示意性地示出了一种根据本发明的实施例的用于在凹陷特征中进行选择性金属形成的方法。金属可以例如选自由Ru金属、Co金属和W金属组成的组。图案化衬底1包含围绕在第一层100中形成的凹陷特征110的场区域101。凹陷特征110包含侧壁103和具有暴露表面104的第二层102。
根据一个实施例,第一层100可以包括介电材料,并且第二层102可以包括金属层。介电材料可以例如包含SiO2,比如氟化硅玻璃(FSG)的低介电常数(低k)材料,碳掺杂氧化物,聚合物,含SiCOH的低k材料,非多孔低k材料,多孔低k材料,CVD低k材料,旋涂介电(SOD)低k材料,或任何其他合适的介电材料、包括高介电常数(高k)材料。在一些示例中,凹陷特征110的宽度(临界尺寸(CD))可以在约10nm和约100nm之间、在约10nm和约15nm之间、在约20nm和约90nm之间、或在约40nm和约80nm之间。在一些示例中,凹陷特征110的深度可以在约40nm和约200nm之间、在约50nm和约150之间、或在约50nm和约150nm之间。在一些示例中,凹陷特征110可以具有在约2和约20之间、或在约4和约6之间的纵横比(深度/宽度)。第二层102可以包括低电阻率金属,比如Cu金属、Ru金属、Co金属、W金属或它们的组合。在一个示例中,第二层102可以包括两个或更多个堆叠金属层。堆叠金属层的示例包括在Cu金属上的Co金属(Co/Cu)和在Cu金属上的Ru金属(Ru/Cu)。
该方法包括用表面改性剂预处理图案化衬底1,该表面改性剂吸附在第一层100上,从而相对于在第一层100上(包括在侧壁103上和场区域101上)增大在第二层102上的金属沉积选择性。表面改性剂的存在阻碍了金属层在第一层100上的沉积,但第二层102未被改性。根据一个实施例,通过暴露于包含能够在衬底上形成自组装单层(SAM)的分子的反应气体,图案化衬底1用表面改性剂预处理。SAM是通过吸附而在衬底表面上自发形成并且被组织成或多或少的大有序域的分子组装体。SAM可以包括具有头部基团、尾部基团和官能端基的分子,并且SAM是在室温或高于室温通过气相将头部基团化学吸附到衬底上、然后缓慢组织尾部基团而产生的。最初,在表面上的小分子密度下,被吸附物分子要么形成无序的分子团,要么形成有序的二维“躺下相”,并且在几分钟至几小时的时间段内以较高的分子覆盖范围开始在衬底表面上形成三维晶体或半晶体结构。头部基团与衬底组装在一起,而尾部基团远离衬底组装。根据一个实施例,形成SAM的分子的头部基团可以包括硫醇、硅烷或膦酸盐。硅烷的示例包括包含C、H、Cl、F和Si原子或C、H、Cl和Si原子的分子。该分子的非限制性示例包括全氟癸基三氯硅烷(CF3(CF2)7CH2CH2SiCl3)、全氟癸硫醇(CF3(CF2)7CH2CH2SH)、氯癸基二甲基硅烷(CH3(CH2)8CH2Si(CH3)2Cl)和特丁基(氯)二甲基硅烷((CH3)3CSi(CH3)2Cl))。
根据本发明的一些实施例,反应气体可以包含含硅气体,包括烷基硅烷、烷氧基硅烷、烷基烷氧基硅烷、烷基硅氧烷、烷氧基硅氧烷、烷基烷氧基硅氧烷、芳基硅烷、酰基硅烷、芳基硅氧烷、酰基硅氧烷、硅氮烷、或它们的任何组合。根据本发明的一些实施例,反应气体可以选自二甲基硅烷二甲胺(DMSDMA)、三甲基硅烷二甲胺(TMSDMA)、双(二甲氨基)二甲基硅烷(BDMADMS)和其他烷基胺硅烷。根据其他实施例,反应气体可以选自N,O双三甲基硅烷基三氟乙酰胺(BSTFA)和三甲基甲硅烷基吡咯(TMS-吡咯)。
根据本发明的一些实施例,反应气体可以选自硅氮烷化合物。硅氮烷是饱和的硅氮氢化物。它们在结构上与硅氧烷类似,用--NH--替换了--O--。有机硅氮烷前体可以进一步包含键合到Si原子的至少一个烷基。烷基可以是例如甲基、乙基、丙基或丁基、或它们的组合。此外,烷基可以是环状烃基,比如苯基。另外,烷基可以是乙烯基。二硅氮烷是具有附接到硅原子的1至6个甲基的化合物、或具有附接到硅原子的1至6个乙基的化合物、或是具有附接到硅原子的甲基和乙基的组合的二硅氮烷分子。
该方法进一步包括通过气相沉积将金属层106a沉积在图案化衬底1上,其中金属层106a优先地沉积在凹陷特征110中的第二层102上。金属层106a可以例如选自由Ru金属、Co金属和W金属组成的组。根据本发明的一个实施例,Ru金属可以通过化学气相沉积(CVD)或原子层沉积(ALD)进行沉积。含Ru前体的示例包括Ru3(CO)12、(2,4-二甲基戊二烯基)(乙基环戊二烯基)钌(Ru(DMPD)(EtCp))、双(2,4-二甲基戊二烯基)钌(Ru(DMPD)2)、4-二甲基戊二烯基)(甲基环戊二烯基)钌(Ru(DMPD)(MeCp))和双(乙基环戊二烯基)钌(Ru(EtCp)2)、以及这些和其他前体的组合。
如图1B中示意性所示,金属沉积可以不是完全选择性的,并且金属核107a可以沉积在侧壁103和场区域101上。与金属层106a不同,金属核107a可以形成非连续层,其中金属核107a中金属的总量小于金属层106a中金属的量。
在一个示例中,Ru金属通过使用CO载气中的Ru3(CO)12前体的CVD沉积。在用表面改性剂预处理衬底后,在厚度约15至20nm的Ru金属沉积在介电材料的凹陷特征底部的Cu金属层上后,在介电材料上观察到Ru金属核。这展示了在不同材料上的Ru金属沉积的有限选择性以及在介电表面上开始Ru金属沉积之前用Ru金属以深于约15至20nm选择性地沉积和填充凹陷特征的困难。观察到通过CVD执行的Ru金属沉积速率按以下顺序减小:金属>金属氮化物或氮化的金属氧化物>金属氧化物或氧化的金属氮化物>ILD,其中Ru金属沉积速率在金属表面上最高并且在ILD表面上最低。这可以用于不同材料上的优先Ru金属沉积。ILD包括包含硅、碳或硅和碳二者的介电化合物。示例包括SiU2、SiON、SiN、SiCOH、Si、SiC和C。
该方法进一步包括从图案化衬底1中移除金属核107a,以在凹陷特征110中的第二层102上选择性地形成金属层106a。这在图1C中示意性地示出。可以优选的是,在金属核107a变得太大并且更难以高效地移除之前,执行金属核的移除。在一个示例中,可以通过使用反应离子蚀刻(RIE)、例如使用等离子体激发的O2气体并且可选地加入含卤素气体(例如,C12)来除去Ru金属核107a。
预处理、沉积和移除的步骤可以重复至少一次以增加沉积在凹陷特征110中的金属的厚度。这在图1D中示意性地示出,其中附加金属层106b优先地沉积在金属层106a上,并且附加金属核107b沉积在侧壁103和场区域101上。此后,如图1E所示,移除附加金属核107b。在一个示例中,可以重复预处理、沉积和移除,直到凹陷特征110用金属完全填充。这在图1F中示意性地示出,其中凹陷特征110用金属层106a至106c填充。
用于凹陷特征中的选择性Ru金属形成的过程示例包括使用TMSDMA气体暴露(其中TMSDMA液体蒸发并用N2气体稀释)、在约180℃和约250℃之间的衬底温度、约5托的处理室压力、以及没有等离子体激发的10秒暴露时间的预处理。Ru金属CVD过程包括包含Ru3(CO)12+CO(例如,气体流量比约为1∶100)的处理气体,在约135℃和约180℃之间(例如约160℃)的衬底温度、在约1毫托和约20毫托之间(例如约5毫托)的处理室压力、以及没有等离子体激发的400秒暴露(其在金属表面上沉积约20nm的Ru金属)。Ru金属移除过程包括使用包含O2和Cl2(例如,气体流量比约为100:1)的蚀刻气体、在约室温和约370℃之间(例如约370℃)的衬底温度、使用电容性耦合的等离子体源的等离子体激发(其中约1200W的RF功率施加到顶部电极并且在约0W和约300W之间(例如0W)的RF功率施加到底部电极(衬底支架)、约5毫托的处理室压力以及40秒暴露时间以移除约5nm的Ru金属核的等效物。
图7示出了在图案化衬底上的凹陷特征中具有选择性Ru金属形成的SEM图像。原始的图案化衬底在W金属膜上包含凸起的SiO2特征。凸起的SiO2特征为约113nm高、约31nm宽,并且间隔约87nm。凸起的SiO2特征形成约113nm深并且宽度约为87nm的凹陷特征。该图示出了沉积过程之后的结果,该沉积过程包括用包含TMSDMA的表面改性剂预处理图案化衬底、使用Ru3(CO)12+CO的Ru金属CVD沉积步骤以及使用等离子体激发的O2气体+Cl2气体的从凹陷特征的侧壁中移除Ru金属核的Ru金属蚀刻步骤。预处理、Ru金属沉积和Ru金属核移除的序列执行四次。该图展示了Ru金属选择性地形成在凹陷特征中,并且在凹陷特征的侧壁上或在蚀刻的SiO2特征的顶表面上不存在Ru金属核。形成在凹陷特征中的Ru金属的厚度约为69nm并填充凹陷特征的体积的约61%。
图2A至图2F示意性地示出了一种根据本发明的另一实施例的用于在凹陷特征中选择性金属形成的方法。图1A已经再现为图2A中的图案化衬底2。该方法包括提供图案化衬底2,该图案化衬底包含形成在第一层100中的凹陷特征110和暴露在凹陷特征110中的第二层102。如图2B所示,该方法包括在图案化衬底2上(包括在凹陷特征110中和围绕凹陷特征110的场区域101)沉积含金属层111。含金属层111可以是适形的,并且在一些示例中,含金属层111可以包括金属氧化物、金属氮化物或它们的组合。金属氧化物可以例如包括Al2O3、TiO2、HfO2、、或MnO2,并且金属氮化物可以例如包括AlN、TiN、HfN或MnN。
此后,如图2C所示,该方法进一步包括从凹陷特征110的底部和从围绕凹陷特征110的场区域101各向异性地移除金属层111,以在凹陷特征110的侧壁103上形成含金属层111。该方法进一步包括用表面改性剂预处理图案化衬底2,该表面改性剂吸附在第一层100上、包括吸附在场区域101上,从而相对于在第一层100上的金属沉积选择性增大在凹陷特征110的侧壁103上和在第二层102上的含金属层111上的金属沉积选择性。
该方法进一步包括通过气相沉积将金属层112沉积在图案化衬底2上,其中金属层112相对于在围绕凹陷特征110的场区域101上优先地沉积在侧壁103上的含金属层111上和凹陷特征110底部的第二层102上。金属层112可以例如选自由Ru金属、Co金属和W金属组成的组。如图2D中示意性所示,金属沉积可能不是完全选择性的,并且金属核113可以沉积在场区域101上。与金属层112不同,金属核113可以形成非连续层,其中金属核113中的金属的总量小于金属层112中的金属的量。根据图2D所示的实施例,金属层112可以完全填充凹陷特征110。如图2E所示,该方法进一步包括将沉积在第一层100的围绕凹陷特征110的场区域101上的金属核113移除,以在凹陷特征110中选择性地形成金属层112。
根据另一实施例,金属层112可以不完全填充凹陷特征110,并且预处理、沉积和移除可以重复至少一次以增加沉积在凹陷特征110中的金属的厚度。根据一个实施例,可以重复预处理、沉积和移除,直到凹陷特征110用金属完全填充为止。
图3A至图3E示意性地示出了一种根据本发明的另一实施例的用于在凹陷特征中选择性金属形成的方法。图1A已经再现为图3A中的图案化衬底3。该方法包括提供图案化衬底3,该图案化衬底包含形成在材料中的凹陷特征110。在一个示例中,材料可以包括第一层100和暴露在凹陷特征110中的第二层102。如图3B所示,该方法进一步包括在图案化衬底3上(包括在凹陷特征110中和围绕凹陷特征110的场区域101上)沉积金属氮化物层114。金属氮化物层114可以是适形的,并且在一些示例中,金属氮化物层114可以包括AlN、TiN、HfN或MnN。
此后,该方法进一步包括氧化场区域101上的金属氮化物层114以形成氧化的金属氮化物层115。如本文所使用的,氧化过程将氧至少并入金属氮化物层114的表面区域中。如图3C中示意性所示,金属氮化物层114也可以在凹陷特征110中在凹陷特征110的开口附近被氧化。可以使用等离子体激发的U2气体执行氧化金属氮化物层114的步骤,其中凹陷特征110的小开口限制了等离子体激发的U2气体渗透到凹陷特征110中。这将金属氮化物层114的氧化限制于场区域101和凹陷特征110的上部。
该方法进一步包括通过气相沉积在衬底上沉积金属层116,其中金属层116优先地沉积在凹陷特征110中未被氧化的金属氮化物层114上。优先的金属沉积被认为是由于金属沉积在金属氮化物层114上相对于在氧化的金属氮化物层115上的孵化时间较短。如图3D中示意性所示,金属沉积可能不是完全选择性的,并且金属核123可以沉积在场区域101上。与金属层116不同,金属核123可以形成非连续层,其中金属核123中的金属的总量小于金属层116中的金属的量。
根据图3D所示的实施例,金属层116可以完全填充凹陷特征110,其中避免了金属氮化物层114的氧化。如图3E所示,该方法进一步包括将沉积在第一层100的围绕凹陷特征110的场区域101上的金属核123移除,以在凹陷特征110中选择性地形成金属层116。
根据另一实施例,金属层116可以不完全填充凹陷特征110,其中避免了金属氮化物层114的氧化,并且沉积和移除的步骤可以重复至少一次以增加沉积在凹陷特征110中的金属层116的厚度。根据一个实施例,可以重复沉积和移除的步骤,直到凹陷特征110用金属层116完全填充为止。
图4A至图4F示意性地示出了一种根据本发明另一实施例的用于在凹陷特征中选择性金属形成的方法。图1A已经再现为图4A中的图案化衬底4。该方法包括提供图案化衬底4,该图案化衬底包含形成在材料中的凹陷特征110。在一个示例中,材料可以包括第一层100和暴露在凹陷特征110中的第二层102。如图4B所示,该方法进一步包括在图案化衬底4上(包括在凹陷特征110中和围绕凹陷特征110的场区域101上)沉积金属氧化物层117。金属氧化物层117可以是适形的,并且在一些示例中,金属氧化物层117可以包括Al2O3、TiO2、HfO2或MnO2。
此后,该方法进一步包括氮化场区域101上和凹陷特征110中的金属氧化物层117,以形成氮化的金属氧化物层118。如本文所使用的,氮化过程将氮至少并入金属氧化物层117的表面区域中。如图4C中示意性所示,氮化的金属氧化物层118可以是适形的。氮化金属氧化物层117的步骤可以使用热氮化过程(例如,不存在等离子体的NH3退火)执行,该热氮化过程有效地氮化整个金属氧化物层117的厚度的至少一部分(包括在凹陷特征110中)。
此后,该方法进一步包括氧化场区域101上的氮化的金属氧化物层118以形成氧化的氮化金属氧化物层119。如本文所使用的,氧化过程将氧至少并入氮化的金属氧化物层118的表面区域中。氧化氮化的金属氧化物层的步骤可以使用等离子体激发的O2气体执行,其中凹陷特征110的小开口限制了等离子体激发的O2气体渗透到凹陷特征110中。这将氮化的金属氧化物层的氧化限制于场区域101和凹陷特征110的上部。这在图4D中示意性地示出。
该方法进一步包括通过气相沉积将金属层120沉积在图案化衬底4上,其中金属层120优先地沉积在凹陷特征110中未被氧化的氮化的金属氧化物层118上。优先的金属沉积被认为是由于金属沉积在氮化的金属氧化物层上相对于在氧化的氮化金属氧化物层119上的孵化时间较短。
如图4E中示意性所示,金属沉积可以不是完全选择性的,并且金属核121可以沉积在场区域101上的氧化的氮化金属氧化物层119上。与金属层120不同,金属核121可以形成非连续层,其中金属核121中的金属的总量小于金属层120中的金属的量。
根据图4E所示的实施例,金属层120可以完全填充凹陷特征110,其中避免了氮化的金属氧化物层118的氧化。如图4F所示,该方法进一步包括将沉积在第一层100的围绕凹陷特征110的场区域101上的金属核121移除,以在凹陷特征110中选择性地形成金属层120。
根据另一实施例,金属层120可以不完全填充凹陷特征110,其中避免了氮化的金属氧化物层118的氧化,并且沉积和移除的步骤可以重复至少一次以增加沉积在凹陷特征110中的金属层120的厚度。根据一个实施例,可以重复沉积和移除的步骤,直到凹陷特征110用金属层120完全填充为止。
图5A至图5D示意性地示出了一种根据本发明另一实施例的用于在凹陷特征中选择性金属形成的方法。图5A示出了图案化衬底5,该图案化衬底包含形成在材料500中的凹陷特征510,其中凹陷特征包含侧壁503和底部502。该方法包括在图案化衬底5上(包括在凹陷特征510中和围绕凹陷特征510的场区域501上)沉积金属氧化物层504。这在图5B中示意性地示出。
该方法进一步包括氮化场区域101上的金属氧化物层504。如本文所使用的,氮化过程将氮至少并入金属氧化物层504的表面区域中以形成氮化的金属氧化物层505。这在图5C中示意性地示出。氮化金属氧化物层504的步骤可以使用等离子体激发的含氮气体(例如,N2或NH3)执行,其中凹陷特征510的小开口限制了等离子体激发的含氮气体渗透到凹陷特征510中。
该方法进一步包括通过气相沉积将金属层506沉积在图案化衬底5上,其中金属层506优先地沉积在场区域501上的氮化的金属氧化物层505上。如图5D中示意性所示,金属沉积可以不是完全选择性的,并且金属核507可以沉积在凹陷特征510中的金属氧化物层504上。
该方法进一步包括将沉积在凹陷特征510中的金属核507移除,以在场区域501上选择性地形成金属层506。这在图5E中示意性地示出。沉积和移除的步骤可以重复至少一次以增加金属层506在场区域501上的厚度。
图6A至图6D示意性地示出了一种根据本发明的另一实施例在凹陷特征中选择性金属形成的方法。在一个示例中,如图6A所示,图案化衬底6可以包括3D NAND器件的一部分。该方法包括提供图案化衬底6,该图案化衬底包含材料600中的蚀刻的竖直特征610和蚀刻的水平特征601。蚀刻的竖直特征610可以是渐缩的,在顶部附近比底部附近具有较大的开口。在一个示例中,材料600可以包括SiO2或SiN。该方法进一步包括氮化蚀刻的竖直特征610和蚀刻的水平特征601以形成氮化层602。氮化的过程可包括热氮化过程(例如,不存在等离子体的NH3退火),该热氮化过程氮化蚀刻的竖直特征610和蚀刻的水平特征601二者。此后,该方法包括等离子体处理(例如,Ar等离子体),该等离子体处理从蚀刻的竖直特征610移除氮化层602,而保持蚀刻的水平特征601中的氮化层602。所得到的图案化衬底6如图6B所示。该方法进一步包括通过气相沉积将金属层603沉积在图案化衬底6上,其中金属层603相对于在蚀刻的竖直特征610上优先地沉积在蚀刻的水平特征601中的氮化层602上。这如图6C所示。执行气相沉积,直到蚀刻的竖直特征610也用金属层604完全填充为止。选择性金属沉积是由于在氮化层602上比在未氮化的蚀刻的竖直特征610上更高的金属沉积速率。这允许蚀刻的竖直特征610和蚀刻的水平特征601的没有任何空隙的完整金属填充。
在各种实施例中已经披露了一种用于用低电阻率金属填充半导体器件中的凹陷特征的方法。为了说明和描述的目的,已经呈现了对本发明的实施例的前述描述。并不旨在穷举或将本发明限制于所披露的确切形式。本说明书和所附权利要求包括仅用于描述目的并且不应解释为进行限制的术语。相关领域的技术人员可以理解,根据以上教导,许多修改和变化是可能的。本领域技术人员将认识附图中示出的各种部件的各种等效组合和替代。因此,意图是本发明的范围不受该详细描述限制,而是由在此所附的权利要求限制。
Claims (22)
1.一种用于形成半导体器件的方法,该方法包括:
提供图案化衬底,该图案化衬底包含形成在第一层中的凹陷特征和暴露在该凹陷特征中的第二层;
用表面改性剂预处理该衬底,该表面改性剂相对于在该第一层上的金属沉积选择性增大在该第二层上的金属沉积选择性;
通过气相沉积将金属层沉积在该衬底上,其中该金属层优先地沉积在该凹陷特征中的该第二层上;以及
移除沉积在该第一层上、包括沉积在场区域上和该第一层的位于该凹陷特征中的侧壁上的金属核,以在该凹陷特征中的该第二层上选择性地形成该金属层。
2.如权利要求1所述的方法,进一步包括:
重复该预处理、沉积和移除至少一次以增加该金属层在该凹陷特征中的厚度。
3.如权利要求1所述的方法,其中,该预处理包括在该第一层上形成自组装单层(SAM)。
4.如权利要求1所述的方法,其中,该金属层选自由Ru金属、Co金属和W金属组成的组,并且该第二层选自由Cu金属、Ru金属、Co金属、W金属和它们的组合组成的组。
5.一种用于形成半导体器件的方法,该方法包括:
提供图案化衬底,该图案化衬底包含形成在第一层中的凹陷特征和暴露在该凹陷特征中的第二层;
将含金属层沉积在该衬底上,包括沉积在该凹陷特征中;
从该凹陷特征的底部并从围绕该凹陷特征的场区域各向异性地移除该含金属层,以在该凹陷特征的侧壁上形成该含金属层;
用表面改性剂预处理该衬底,该表面改性剂相对于在该第一层上的金属沉积选择性增大在该凹陷特征的侧壁上和该第二层上的该含金属层上的金属沉积选择性;
通过气相沉积将金属层沉积在该衬底上,其中该金属层相对于在围绕该凹陷特征的场区域上优先地沉积在这些侧壁上和该凹陷特征中的该第二层上的该含金属层上;以及
移除沉积在该场区域上的金属核,以在该凹陷特征中选择性地形成该金属层。
6.如权利要求5所述的方法,进一步包括:
重复该预处理、沉积和移除至少一次以增加该金属层在该凹陷特征中的厚度。
7.如权利要求5所述的方法,其中,该预处理包括在该第二层上形成自组装单层(SAM)。
8.如权利要求5所述的方法,其中,该金属层选自由Ru金属、Co金属和W金属组成的组,并且该第二层选自由Cu金属、Ru金属、Co金属、W金属和它们的组合组成的组。
9.如权利要求5所述的方法,其中,该含金属层包含金属氧化物、金属氮化物或它们的组合。
10.如权利要求5所述的方法,其中,该金属氧化物包括Al2O3、TiU2、HfO2或MnU2,并且该金属氮化物包括AlN、TiN、HfN或MnN。
11.一种用于形成半导体器件的方法,该方法包括:
提供包含形成在材料中的凹陷特征的图案化衬底;
将金属氮化物层沉积在该衬底上,包括沉积在该凹陷特征中和围绕该凹陷特征的场区域上;
氧化该场区域上的该金属氮化物层;
通过气相沉积将金属层沉积在该衬底上,其中该金属层优先地沉积在该凹陷特征中未被氧化的该金属氮化物层上;以及
移除沉积在该场区域上的金属核,以在该凹陷特征中选择性地形成该金属层。
12.如权利要求11所述的方法,进一步包括:
重复该沉积和移除至少一次以增加该金属层在该凹陷特征中的厚度。
13.如权利要求11所述的方法,其中,该金属层选自由Ru金属、Co金属和W金属组成的组。
14.如权利要求11所述的方法,其中,该金属氮化物层包括AlN、TiN、HfN或MnN。
15.一种用于形成半导体器件的方法,该方法包括:
提供包含形成在材料中的凹陷特征的图案化衬底;
将金属氧化物层沉积在该衬底上,包括沉积在该凹陷特征中和围绕该凹陷特征的场区域上;
氮化该场区域上和该凹陷特征中的该金属氧化物层;
氧化该场区域上的氮化的金属氧化物层;
通过气相沉积将金属层沉积在该衬底上,其中该金属层优先地沉积在该凹陷特征中未被氧化的该氮化的金属氧化物层上;以及
移除沉积在该场区域上的金属核,以在该凹陷特征中选择性地形成该金属层。
16.如权利要求15所述的方法,进一步包括:
重复该沉积和移除至少一次以增加该金属层在该凹陷特征中的厚度。
17.如权利要求15所述的方法,其中,该金属层选自由Ru金属、Co金属和W金属组成的组。
18.如权利要求15所述的方法,其中,该金属氧化物层包括Al2O3、TiO2、HfU2或MnU2。
19.一种用于形成半导体器件的方法,该方法包括:
提供包含形成在材料中的凹陷特征的图案化衬底;
将金属氧化物层沉积在该衬底上,包括沉积在该凹陷特征中和围绕该凹陷特征的场区域上;
氮化该场区域上的该金属氧化物层;
通过气相沉积将金属层沉积在该衬底上,其中该金属层优先地沉积在该场区域中的氮化的金属氧化物层上;以及
移除沉积在该凹陷特征中的金属核,以在该场区域上选择性地形成该金属层。
20.如权利要求19所述的方法,进一步包括:
重复该沉积和移除至少一次以增加该金属层在该场区域上的厚度。
21.如权利要求19所述的方法,其中,该金属层选自由Ru金属、Co金属和W金属组成的组。
22.如权利要求19所述的方法,其中,该金属氧化物层包括Al2O3、TiO2、HfO2或MnO2。
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- 2019-10-10 JP JP2021519654A patent/JP7406684B2/ja active Active
- 2019-10-10 WO PCT/US2019/055676 patent/WO2020077112A1/en active Application Filing
- 2019-10-10 KR KR1020217012312A patent/KR20210057185A/ko not_active Application Discontinuation
- 2019-10-10 US US16/598,772 patent/US11024535B2/en active Active
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2021
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JP7406684B2 (ja) | 2023-12-28 |
WO2020077112A1 (en) | 2020-04-16 |
TW202029286A (zh) | 2020-08-01 |
US20210287936A1 (en) | 2021-09-16 |
JP2022504574A (ja) | 2022-01-13 |
US20200118871A1 (en) | 2020-04-16 |
KR20210057185A (ko) | 2021-05-20 |
US11621190B2 (en) | 2023-04-04 |
US11024535B2 (en) | 2021-06-01 |
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