CN107492481A - 用于在较低温度下使用远程等离子体源进行选择性氧化的设备和方法 - Google Patents
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Abstract
本文描述用于选择性地氧化硅的装置和方法。用于对暴露的硅表面进行选择性氧化的设备包括:热处理腔室,所述热处理腔室具有多个壁、第一入口连接件和第二入口连接件,其中壁界定处理腔室内的处理区域;处理腔室内的基板支撑件;与第一入口连接件连接的氢源;与氢源连接的热源;和与第二入口连接件和氧源连接的远程等离子体源。一种用于对非金属表面进行选择性氧化的方法,所述方法可包括:在小于800℃的温度下的处理腔室中定位基板;使氢流入处理腔室中;产生含氧远程等离子体;在处理腔室中将远程等离子体与氢气混合以产生活性处理气体;和使基板暴露于活性气体。
Description
本申请是申请日为2013年7月25日、申请号为201380040767.0、发明名称为“用于在较低温度下使用远程等离子体源进行选择性氧化的设备和方法”的发明专利申请的分案申请。
技术领域
本发明的实施方式大体涉及用于选择性地氧化硅的设备和方法。
背景技术
硅的氧化对CMOS制造而言是基本的技术。用于硅的氧化的最常见方法依赖于在O2、H2O/H2、H2O/O2、O2/H2或上述各者的组合的环境中的热处理。在IC制造中用以提供硅氧化处理的硬件是分批热熔炉(batch thermal furnace)和RTP。在传统的氧化系统和处理中,需要高温(700℃以上)来为在硅或多晶硅上的氧化物生长提供活化能。
先进的集成电路制造需要数个处理步骤,在所述步骤中,氧化硅薄膜在硅或多晶硅结构上生长。对于一些应用,氧化处理必须是选择性的,以使包括钨在内的其他材料不被氧化。目前,在高温(大于700℃)下的在O2、H2O/H2或H2O/O2任一环境中的热处理被用以执行此氧化处理。
为达到氧化物的生长速率以使处理实际有效,高温是必需的,并且在一些情况下,氧化物质量需要高温。然而,下一代装置中的许多装置如果在工艺流程中需要氧化物生长的地方暴露于高温和氧化环境的组合,则这些装置将经受严重损坏。由此,本领域中需要允许在不氧化其他表面材料的情况下进行硅的低温选择性氧化的方法和设备。
发明内容
本发明的实施方式大体涉及硅的选择性氧化方法。在一个实施方式中,用于对暴露的硅表面进行选择性氧化的设备可包括:具有多个壁的热处理腔室,所述热处理腔室具有第一入口连接件和第二入口连接件,其中所述多个壁界定处理腔室内的处理区域;处理腔室内的基板支撑件;与处理腔室的第一入口连接件流体连接的氢源;与氢源连接的热源;与处理腔室的第二入口连接件流体连接的远程等离子体源;和与远程等离子体源流体连接的氧源。在一些实施方式中,流体连接件可包括管件,所述管件包括惰性材料。
在另一个实施方式中,用于对非金属表面进行选择性氧化的方法可包括:在处理腔室中定位基板,其中将所述处理腔室维持在低于800℃的温度下;使氢流入处理腔室;产生含氧的远程等离子体;使远程等离子体流入处理腔室,其中所述远程等离子体与氢气混合以产生活性处理气体;和使基板暴露于活性气体。
在另一个实施方式中,用于对非金属表面进行选择性氧化的方法可包括:在处理腔室中定位基板,其中将所述处理腔室维持在低于800℃的温度下;使氢流动接近热线设备(hot wire apparatus)以产生活性氢;使活性氢流入处理腔室中;产生含氧的远程等离子体;在处理腔室中将远程等离子体与氢气混合以产生活性处理气体;将基板暴露于活性气体以氧化所需量的硅,其中所述活性气体氧化硅表面并还原金属表面;和冷却基板。
附图说明
可通过参照实施方式(所述实施方式中的一些实施方式描绘于附图中)来详细理解本发明的上述特征以及上文简要概述的有关本发明更为具体的描述。然而,应注意,附图仅图示本发明的典型实施方式,因此不应将附图视为限制本发明的范围,因为本发明可允许其他同等有效的实施方式。
图1是根据一个实施方式的具有远程等离子体源的热处理腔室的示意图。
图2是根据一个实施方式的选择性氧化方法的框图。
图3A和图3B是利用和未利用预烘烤(pre-baking)实现的选择性氧化和还原的图解表示图。
为了便于理解,在可能的情况下,已使用相同的参考数字来标示各图中共有的相同元件。预期一个实施方式中所披露的元件可有利地用于其他实施方式,而无需具体详述。
具体实施方式
本发明的实施方式大体涉及硅的选择性氧化方法。更具体而言,实施方式涉及硅的选择性氧化和用于去除原生氧化物(native oxide)的钨的选择性还原。
在先进的CMOS装置中,硅相对于钨的选择性氧化是用于修复由于在SiO2电介质上的钨栅电极周围进行的离子注入或反应离子蚀刻(RIE)而造成的氧化硅损坏的重要工艺。本文所述的实施方式可用以在快速热处理(RTP)腔室或热熔炉中通过利用远程等离子体和热处理的组合对硅相对于其他非金属进行选择性地氧化。
本文并不意在受理论约束,在硅氧化期间引起的吉布斯自由能变化大于在钨氧化期间的吉布斯自由能变化,因此导致硅相对于钨的选择性氧化。在现有技术的氧化工艺中,反应涉及在高温和高压下输送至基板的氢和氧的水蒸汽或燃烧。高温可使钨晶须化(whiskering),晶须化是来自钨的长晶体结构的形成,所述晶须化对装置性能可能是有害的。考虑到钨的晶须化,利用较低温度的选择性氧化将更有利于整体装置性能。
下面参照附图更明确地描述本发明的实施方式。
图1是根据一个实施方式的RTP腔室,所述RTP腔室具有远程等离子体源。本发明的实施方式所使用的RTP腔室可为能够在维持基板周围的大气条件的同时加热和冷却基板的任何类型的RTP腔室,诸如Centura热处理系统或Vantage RTP系统,上述系统可从位于美国加利福尼亚州圣克拉拉市(Santa Clara,CA)的应用材料公司(Applied Materials,Inc.)购得。可以设想,在不背离本发明的范围的前提下,包括来自其他制造商的腔室的其他热处理腔室也可用于本发明的实施方式。
RTP腔室可使用来自电阻热的加热,诸如在基板支撑件中形成的电阻加热元件;使用来自辐射热的加热,诸如来自加热灯的加热;或使用来自辐射能的加热,诸如来自激光退火系统的加热。
处理腔室100通常包括腔室主体101,所述腔室主体101界定处理区域110,基板102可在所述处理区域110中被热处理。基板102被安置在基板支撑件112上,所述基板支撑件112可帮助界定处理区域110。能量源103被配置成将辐射能105导向处理区域110。传感器108被设置在适当的位置以测量腔室主体101的内部中的部件的属性。在一个实施方式中,传感器108被配置成通过获得和测量来自基板102的辐射能而测量基板102的温度。传感器108可连接至系统控制器109,所述系统控制器109可被用来根据来自传感器108的测量结果而调整能量源103。
远程等离子体源120与处理腔室100相连接。用于本发明的实施方式的远程等离子体源可为能够被用来形成至少含氧的远程等离子体的任何类型的远程等离子体源,诸如可从位于美国马萨诸塞州安多佛市(Andover,MA)的MKS Instruments购得的R*evolutionIII远程RF等离子体源。可以设想,在不背离本发明的范围的前提下,包括来自其他制造商的腔室的其他远程等离子体腔室也可用于本发明的实施方式。
远程等离子体源120通过第一管件122流体耦接至处理腔室100,所述第一管件122可能是视线管件(line of sight tubing)。氧气源126亦流体耦接至远程等离子体源120,诸如感应耦合远程等离子体源。进一步的实施方式可包括惰性气体源128,所述惰性气体源128与远程等离子体源120耦接,以便产生可被输送到处理腔室100的处理区域110的氧气/惰性气体等离子体。
第一管件122将远程等离子体源120流体耦接至处理腔室100。在本文中使用的术语“视线”是指在远程等离子体源120与处理腔室100之间传输一段短距离,以便使自由基复合(recombination)或吸附到管件表面上的可能性降至最低。第一管件122可包括惰性材料,诸如蓝宝石、石英或其他陶瓷材料,以防止由远程等离子体源120提供的氧自由基的吸附和/或复合。第一管件122可被配置成为在远程等离子体源120中产生的氧自由基进入处理腔室100中提供直接的短路径。
氢气源124连接至处理腔室100。氢气源124将氢气输送至处理区域110,在所述处理区域110处,氢气将被含氧的远程等离子体活化,所述含氧的远程等离子体是从远程等离子体源120输送来的。热线设备130被可选择性地安置在氢气源124与处理腔室100之间。在使用热线设备130的实施方式中,氢气可流过热线设备130的热丝,所述热丝在将氢输送至腔室中之前活化氢。此外,热线设备130可利用第二管件132连接至处理腔室,所述第二管件132诸如视线管件。第一管件122的组成和参数可用于第二管件132。
温度控制对于在形成氧化硅的同时不在钨上形成晶须结构十分重要。因此,用于本文所述的实施方式的RTP腔室应能够将温度控制在500℃与1100℃的范围之间,同时在腔室中快速加热和冷却基板。这种加热和冷却可利用一些结构来执行,所述结构诸如基板支撑件中的加热元件和/或冷却剂口。
图2是根据一个实施方式的选择性氧化方法的框图。方法200可包括在热处理腔室中定位基板,其中将所述基板维持在小于800℃的温度下,如步骤202中所示。在高于800℃的温度下,可能在沉积在基板表面上的钨特征结构上形成钨晶须。随着钨晶须生长,所述晶须可接触附近的特征结构,以及产生不均匀的基板表面。此外,将温度维持在约800℃以下对具有低热预算的应用是有益的。因此,将基板维持在低于约800℃的温度下,及优选地维持在约700℃或低于约700℃的温度下,对半导体装置的整体功能可能是有益的。
方法200可进一步包括使氢流入处理腔室,如步骤204中所示。硅难以通过传统的热氧化在O2或H2O中进行氧化,通常需要极高温度和较长时间。已知以原子氧形式进行氧化,包括由氧等离子体产生的物种。通过利用O2和H2的混合物(包括由等离子体活化的O2)亦可允许硅氧化,同时亦改变硅和诸如钨的其他材料的氧化速率和/或相对速率。
对于位于大小适当的腔室中的300mm基板而言,H2的流量可从约1slm至约10slm(从约3.33sccm/cm2至约33.33sccm/cm2)。可使氢流入腔室以维持1Torr与2Torr之间的整体腔室压力,诸如1.5Torr的整体腔室压力。基板温度可缓降至约550℃与约650℃之间,诸如缓降至约600℃的基板。在一些实施方式中,可将腔室维持在与基板相同的温度下。
进一步的实施方式可包括预浸/预烘烤工艺。在一个实施方式中,使氢(H2)流入处理腔室,所述处理腔室中定位有基板。然后,将基板浸泡在约450Torr与约550Torr之间的压力下的H2中,例如530Torr,同时将基板维持在约700℃的温度下。然后,基板保持浸泡在H2中达较短的一段时间,诸如约45秒与约75秒之间,诸如60秒。相关数据显示,预浸在H2中可有利于氧化硅的形成,同时使形成在钨表面上的原生氧化物还原。
更进一步的实施方式可包括在使H2流入腔室之前使用热线对H2进行活化。在本实施方式中,使H2流过热丝。所述细丝可由抗腐蚀金属或合金组成,诸如钨或钌钨。热丝可在不形成等离子体的情况下活化氢,由此防止发生在作为等离子体使用氢时可见的一些更有害的影响。活性氢将包括H2和离子化氢,使活性氢流入处理腔室,在所述处理腔室中,活性氢既可以从形成于诸如钨的暴露金属表面上的原生氧化物中提取氧,又可以将氧沉积在硅上。已在氢原子百分比从70%至95%观察到钨的还原。
方法200可进一步包括产生含氧的远程等离子体,如步骤206中所示。关于H2形成为远程等离子体存在很多问题。首先,当将H2转变为等离子体时,H2会侵蚀(attack)源和其他腔室部件,诸如由阳极化铝、石英和蓝宝石组成的部件。此反应可导致过早的源故障。此外,与H2的反应可产生沉积前驱物,诸如金属氢化物,所述前驱物可在基板上沉积。通过单独形成氧的远程等离子体,可形成对基板具有最小破坏的氧的活性物种,并且在接触腔室其他部分时不具有氢等离子体的有害影响。此外,活性氧可用以在存在基板的情况下活化氢,以便限制离子化氢/自由基化氢对基板的影响。
对于300cm2基板,使氧气以约1slm至约5slm(从约3.33sccm/cm2至约16.67sccm/cm2)的流量流入远程等离子体源。氧气可与惰性气体混合以形成氧气混合物。惰性气体可包括诸如氩、氦或氪之类的气体。然后,可利用能量源将氧气或混合物转变为等离子体。能量源可为电容式、感应式或微波能量源。
方法200可进一步包括使远程等离子体流入处理腔室,在所述处理腔室中所述远程等离子体与氢气混合以产生活性处理气体,如步骤208中所示。可允许等离子体在流动之前进行淬火,或者是通过视线管成为流入腔室中的等离子体。等离子体与氢在基板之上混合,从而产生Η、O和OH分子。将基板温度维持在550℃与650℃之间(诸如600℃),以利于氧化硅的形成。
在一个实施方式中,在预烘烤步骤中流入腔室的氢可被重复利用为用于活性处理气体的氢气。进一步的实施方式可包括在使氢流入以产生活性气体之前,利用惰性气体或氢气清洁腔室。这些步骤可与氧等离子体的形成同时发生。同样,可使氢在氧等离子体从远程等离子体源流出之前或同时流入腔室,以与氧等离子体在基板之上混合。
方法200可进一步包括使基板暴露于活性气体以氧化硅并还原暴露的金属,诸如钨,如步骤210中所示。由于等离子体中形成的氧自由基的存在,硅的等离子体氧化通常服从对温度具有依赖性的Arrhenius-like,但具有远低于热氧化的活化能。由于氧的活化与随后或同时进行的氢的活化,导致硅被氧化。此外,氢和氧的活性物种可导致钨在相同条件下的还原。
图3A是显示氧化硅在硅基板上的生长增多的实验数据。全部数据是从300mm裸硅基板收集的。基板起初被加热到700℃,随后进行可选的预烘烤步骤。所述可选的预烘烤步骤包括在530Torr的压力下浸泡在H2中达60秒。在预烘烤步骤之后,将温度缓降至600℃,并将压力缓降至1.5Torr。在选择性氧化部分期间,温度维持在600℃。远程等离子体是在将源功率固定在3000W达60秒的情况下由氧产生的,然后使远程等离子体流入腔室,在所述腔室中使远程等离子体与单独流入腔室中的H2混合。腔室中H2与O2的总压力是1.5Torr。
图解表示图示出H2的原子百分比从80%到100%的氧化硅厚度。硅生长在氢原子百分比80%与90%(分别具有20%和10%的氧原子百分比)之间较高。如在进一步的类似实验(本文未示出)中所发现的,氢原子百分比在70%与95%(分别具有30%和5%的氧原子百分比)之间提供最佳的硅上氧化物生长。预烘烤硅基板的氧化硅厚度一贯高于未经烘烤的硅基板,无需升高温度即可提供0.2埃与0.8埃之间的厚度增加。在100%的H2样本中,预烘烤氧化硅明显更高,所述情况可为在有原生氧化物存在的情况下,来自由氢重新分布(redistributed)的分离氧(sequestered oxygen)的氧化物生长。
图3B是显示原生氧化钨的还原的实验数据。全部数据是从300mm硅基板收集的,所述硅基板具有通过CVD工艺沉积的钨。基板起初被加热到700℃,随后进行可选的预烘烤步骤。可选的预烘烤步骤包括在530Torr的压力下浸泡在H2中达60秒。在预烘烤步骤之后,将温度缓降至600℃,并将压力缓降至1.5Torr。在选择性氧化部分期间,将温度维持在600℃。远程等离子体是在将源功率固定在3000W达60秒的情况下由氧产生的,然后使远程等离子体流入腔室,在所述腔室中将远程等离子体与单独流入腔室中的H2混合。腔室中H2和O2的总压力是1.5Torr。
图解表示图示出与没有氧的情况相比,在氢和氧都存在的情况下的原生氧化钨厚度的一般减少。氧化物浓度利用X射线光电子光谱法(XPS)测得。XPS测量结果显示在已沉积钨(原生WOx)中氧百分比为38%至39%。原生WOx含量的减少在氢原子百分比80%与90%(分别具有20%和10%的氧原子百分比)之间较高。如在进一步的类似实验(本文未示出)中所发现的,氢原子百分比在70%与95%(分别具有30%和5%的氧原子百分比)之间可用于原生WOx的还原。与氧化硅厚度相关,与未经烘烤的钨涂覆基板相比,预烘烤的钨涂覆基板的原生WOx一贯更低,从而在无需升高温度的情况下提供2%与3%之间的氧化物还原。在100%的H2样本中,预烘烤的原生WOx更低,此情况证明预烘烤处理在整体原生WOx还原方面是有益的,所述预烘烤处理与氧处理协同地起作用。
尽管先前已经论述,钨可诸如在腔室之间的移送期间通过与大气接触而形成氧化物。这些氧化物可使形成于基板上的钨特征结构的功能退化,并缩短钨特征结构的寿命。因此,去除这些缺陷十分重要。因此,可利用与所教导的用于低温氧化硅生产的工艺和条件相同的工艺和条件来实现减少原生WOx形成的优势。此外,相信通过同一工艺进行的还原钨和氧化硅的组合可通过将氧从原生WOx层中分离并在暴露的硅上形成氧化硅而达到进一步的协同性。
在氢浓度高于80%的情况下,XPS测得的在钨膜中O百分比已由于根据温度、预烘烤条件和RP功率的还原作用而降至31%至33%。因此,得出结论,选择性氧化可在600℃下在腔室中氢浓度的原子百分比至少为80%的情况下实现。本文描述的实验参数并非意在限制,因为如上所述其他温度、压力、流量和装置参数可提供与本文所披露的优势相同的优势。
本文所述的实施方式涉及在还原原生WOx的同时选择性地氧化暴露的硅的设备和方法。在基板处理期间,诸如在NAND闪存装置的形成期间,氧化硅层可能由于诸如蚀刻之类的处理而遭到损坏。此外,如上所示,诸如钨之类的已沉积金属含有原生氧化物,所述原生氧化物可能对装置性能有害。上述设备和方法可在不超过800℃的温度下还原沉积金属上的原生氧化物,同时从暴露的硅形成氧化硅。
尽管前述内容是针对本发明的实施方式,但可在不背离本发明基本范围的前提下设计本发明的其他和进一步的实施方式,并且本发明的范围由以下要求保护的范围确定。
Claims (20)
1.一种设备,所述设备包括:
具有多个壁的处理腔室,所述处理腔室具有第一入口连接件和第二入口连接件,其中所述多个壁界定所述处理腔室内的处理区域;
能量源,所述能量源被安置成将辐射能输送至所述处理区域;
基板支撑件,所述基板支撑件位于所述处理腔室内;
氢源,所述氢源与所述处理腔室的所述第一入口连接件流体连通;
热源,所述热源与所述氢源和所述处理区域连接,所述热源安置在所述氢源与所述处理区域之间;
远程等离子体源,所述远程等离子体源与所述处理腔室的所述第二入口连接件流体连接;和
氧源,所述氧源与所述远程等离子体源流体连接。
2.如权利要求1所述的设备,其中所述热源是热线设备,所述热线设备流体连通在所述氢源与所述处理腔室之间。
3.如权利要求1所述的设备,其中所述热源将所述氢源连接至所述处理腔室的所述第一入口连接件。
4.如权利要求3所述的设备,其中所述热源是热线设备。
5.如权利要求1所述的设备,其中与所述氢源的流体连通包括管件,所述管件包括惰性材料。
6.如权利要求1所述的设备,其中所述能量源产生导向所述基板支撑件的辐射能。
7.如权利要求6所述的设备,其中所述能量源是热灯。
8.如权利要求6所述的设备,其中所述能量源是激光退火系统。
9.如权利要求1所述的设备,其中所述远程等离子体源是感应耦合远程等离子体源。
10.如权利要求1所述的设备,进一步包括与所述远程等离子体源耦接的惰性气体源。
11.如权利要求1所述的设备,其中所述远程等离子体源安置在所述氧源与所述处理腔室之间。
12.如权利要求11所述的设备,其中所述远程等离子体源是感应耦合远程等离子体源。
13.如权利要求1所述的设备,进一步包括在所述基板支撑件中形成的电阻加热元件。
14.一种用于对非金属表面进行选择性氧化的方法,所述方法包括:
在处理腔室中定位基板,其中将所述处理腔室维持在低于800℃的温度下;
使氢流动接近热线设备以产生活性氢;
使所述活性氢流入所述处理腔室中;
产生含氧远程等离子体,其中与氧相比,氢包括至少70%原子百分比;
在所述处理腔室中将所述远程等离子体与氢气混合,以产生活性处理气体;
使所述基板暴露于所述活性气体以氧化所需量的硅,其中所述活性气体氧化硅表面并还原金属表面;和
冷却所述基板。
15.如权利要求14所述的方法,其中氢包括所述活性处理气体的至多95%原子百分比。
16.如权利要求14所述的方法,进一步包括在产生含氧远程等离子体之前将所述基板浸泡在氢中。
17.如权利要求16所述的方法,其中所述浸泡处理维持在600℃与800℃之间的温度下达至少45秒。
18.如权利要求17所述的方法,其中所述浸泡处理维持在约450Torr与约550Torr之间的压力下的氢中。
19.如权利要求14所述的方法,其中氢气的流量从约3.33sccm/cm2至约16.67sccm/cm2。
20.如权利要求14所述的方法,其中氢气的流量从约3.33sccm/cm2至约33.3sccm/cm2。
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KR102065483B1 (ko) | 2020-01-13 |
KR102189015B1 (ko) | 2020-12-09 |
CN107492481B (zh) | 2021-08-13 |
JP6615607B2 (ja) | 2019-12-04 |
JP6993395B2 (ja) | 2022-01-13 |
US20160300712A1 (en) | 2016-10-13 |
JP2020061555A (ja) | 2020-04-16 |
JP6622844B2 (ja) | 2019-12-18 |
KR20200004927A (ko) | 2020-01-14 |
US10714333B2 (en) | 2020-07-14 |
CN104541362B (zh) | 2017-08-01 |
JP2015526903A (ja) | 2015-09-10 |
JP2018142715A (ja) | 2018-09-13 |
CN104541362A (zh) | 2015-04-22 |
US20140034632A1 (en) | 2014-02-06 |
KR20150036768A (ko) | 2015-04-07 |
WO2014022184A1 (en) | 2014-02-06 |
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