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CN111684566A - 用于氮化硅薄膜的处理方法 - Google Patents

用于氮化硅薄膜的处理方法 Download PDF

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CN111684566A
CN111684566A CN201980010113.0A CN201980010113A CN111684566A CN 111684566 A CN111684566 A CN 111684566A CN 201980010113 A CN201980010113 A CN 201980010113A CN 111684566 A CN111684566 A CN 111684566A
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gas
silicon nitride
nitride layer
substrate
processing
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郭津睿
梁璟梅
P·P·杰哈
T·阿肖克
T-J·龚
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Applied Materials Inc
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Abstract

本文的实施例提供使用可流动化学气相沉积(FCVD)工艺沉积的氮化硅层的基于自由基的处理。该FCVD沉积的氮化硅层的基于自由基的处理期望地增加层中稳定的Si‑N键的数目，从该层移除不期望的氢杂质，且期望地提供所得的氮化硅层中的进一步交联、致密化、及氮化(氮的并入)。在一个实施例中，形成氮化硅层的方法包括：将基板定位在基板支撑件上，该基板支撑件设置在处理腔室的处理容积中；以及处理沉积在该基板上的氮化硅层。处理该氮化硅层包括：使第一气体的一种或多种自由基物质流动，该第一气体包括NH3、N2、H2、Ar、He、或前述气体的组合；以及将氮化硅层暴露于该自由基物质。

Description

用于氮化硅薄膜的处理方法
技术领域
本公开的实施例大致上关于半导体组件制造工艺的领域，更具体而言，关于用于在电子组件制造工艺中已沉积于基板表面上的氮化硅层的基于自由基的处理的方法。
背景技术
氮化硅常用作电子组件制造工艺中的介电材料，诸如金属层级之间的绝缘层、防止氧化或其他扩散的阻挡层、硬模、钝化层、诸如用于晶体管中的间隔件材料、抗反射涂层材料、非易失性存储器中的层、以及作为组件特征之间的沟槽中的间隙填充材料(以减少其间的串扰)。经常，在沉积氮化硅层之后，进一步处理该氮化硅层，以达成期望的膜化学计量、蚀刻选择性、以及其它期望的膜性质。常规的处理方法包括，使氮化硅层暴露于高密度等离子体(HDP)。但是，常规的处理方法由于该方法的离子轰击而制造了损坏在基板上的下方特征和材料的风险，或在其他方面不适合用于对设置在高深宽比开口中的氮化硅材料进行处理。
因此，本领域中所需要的是处理所沉积的氮化硅层以达成期望的氮化硅化学计量和其它期望材料特性的改进的方法。
发明内容
本文描述的实施例大致上提供使用可流动化学气相沉积(FCVD)工艺沉积的氮化硅层的基于自由基的处理。在一些实施例中，该方法进一步包括，在进行氮化硅层的处理之前沉积氮化硅层。
在一个实施例中，一种处理基板的方法包括：将基板定位在基板支撑件上，该基板支撑件设置在处理腔室的处理容积中；以及处理已经沉积在该基板上的氮化硅层。处理该氮化硅层包括：使第一气体中的一种或多种自由基物质流动，该第一气体包括NH3、N2、H2、He、Ar、或其组合；以及将氮化硅层暴露于该自由基物质。在一些实施例中，该方法进一步包括沉积该氮化硅层，包括：使一种或多种硅前驱物流进该处理腔室的处理容积；将该基板暴露于该一种或多种硅前驱物；提供包括第二气体的自由基物质的一种或多种自由基共反应物；以及将该基板暴露于该一种或多种自由基共反应物。
在另一个实施例中，一种用于氮化硅层的基于自由基的处理的方法，包括：将基板定位在基板支撑件上，该基板支撑件设置在处理腔室的处理容积中；以及处理已经沉积在该基板上的氮化硅层。处理该氮化硅层包括：使第一气体的一种或多种自由基物质流动，该第一气体包括NH3、N2、H2、He、Ar、或前述气体的组合；以及将所沉积的氮化硅层暴露于该自由基物质。在此，使用一方法沉积该氮化硅层，该方法包括：使一种或多种硅前驱物流进该处理腔室的该处理容积；将该基板暴露于该一种或多种硅前驱物；使包括第二气体的自由基物质的一种或多种自由基共反应物流动；以及将该基板暴露于该一种或多种自由基共反应物。
在另一个实施例中，一种形成氮化硅层的方法包括：沉积氮化硅层以及对沉积的该氮化硅层进行基于自由基的处理。沉积该氮化硅层包括：使一种或多种硅前驱物流进第一处理腔室的处理容积；将该基板暴露于该一种或多种硅前驱物；使包括第一气体的自由基物质的一种或多种自由基共反应物流动；以及将该基板暴露于该一种或多种自由基共反应物。处理所沉积的氮化硅层包括：使第二气体的一种或多种自由基物质流动，该第二气体包括NH3、N2、H2、He、Ar、或前述气体的组合；以及将经沉积的氮化硅层暴露于该第二气体的该自由基物质。
附图说明
通过参考实施例(其中一些在附图中说明)，可以获得上文简要总结的本公开的更具体的描述，如此能够详细地了解本公开的上述特征。然而，应注意，附图仅说明示例性实施例，因此不应认为是对本公开的范围的限制，并且，可允许其他等效的实施例。
图1是可用于实行本文所述方法的示范性处理腔室的示意剖面视图。
图2是阐述用于氮化硅层的基于自由基的处理的方法的流程图。
具体实施方式
本文描述的实施例大致上关于用于对设置在基板表面上的氮化硅层进行基于自由基的处理的方法，具体而言，关于用于已使用可流动化学气相沉积(FCVD)工艺沉积的氮化硅层的基于自由基的处理的方法。当相较于使用常规方法沉积的氮化硅层时，可流动氮化硅工艺(例如，使用(FCVD)工艺沉积的氮化硅层)通常提供改善的高深宽比特征的间隙填充性能。然而，通常由FCVD工艺提供的氮化硅层会不期望地包括Si-H和Si-NH键中的一者或两者的复合网络，并且，相较于常规上所沉积的(不可流动的)氮化硅层，会不期望地提供较低的氮化硅层膜密度。用于改善氮化硅层的膜质量的常规处理方法可以包括，将所沉积的氮化硅层暴露于高密度等离子体(HDP)。不幸的是，HDP处理不期望地使在受处理的层下方的层和特征暴露于来自受处理的层的离子轰击的损害。因此，本文的实施例提供利用气体自由基的FCVD沉积的氮化硅层的处理，其有助于在期望的处理深度处进一步交联、致密化、和氮并入(氮化)至受处理的氮化硅层中。本文提供的方法合乎期望地移除氢杂质并且增加其中的稳定S-N键的数目，而没有使氮化硅层或设置在该氮化硅层下方的特征和材料层暴露于因受处理的层的离子轰击而造成损坏的风险。
图1是可以用于实行本文所述方法的示例性处理腔室的示意剖面视图。在此，处理腔室100特征在于腔室盖组件101、一个或多个侧壁102、以及腔室基座104，其共同限定处理容积120。腔室盖组件101包括腔室盖103、喷头112、以及电绝缘环105，该电绝缘环105设置在腔室盖103和喷头112之间，该腔室盖103、喷头112、以及电绝缘环105限定了气室122。设置成穿过腔室盖103的气体入口114流体耦接至气体源106。在一些实施例中，该气体入口114进一步流体耦接至远程等离子体源107。喷头112具有设置成穿过该喷头112的多个开口118，该喷头112用于将处理气体或气态自由基从气室122穿过该多个开口118均匀分配至处理容积120中。
在一些实施例中，当开关144设置在第一位置(如所示)时，电源供应器142(例如RF或VHF电源供应器)经由开关144电耦接至腔室盖。当开关设置在第二位置(未示出)时，电源供应器142电耦接至喷头112。当开关144处于第一位置时，电源供应器142用于点燃和维持第一等离子体，该第一等离子体在基板115的远程，诸如设置在气室122中的远程等离子体128。该远程等离子体128由流入气室的处理气体所构成，并且通过与来自电源供应器142的电力进行电容耦合，而维持为等离子体。当开关144处于第二位置时，电源供应器142用于在喷头112和配置在基板支撑件127上的基板115之间的处理容积120中点燃并保持第二等离子体(未示出)。
处理容积120通过真空出口113流体耦接至真空源，诸如流体耦接至一个或多个专用真空泵，该真空出口113将处理容积120保持在次大气压的条件下并且从处理空间120抽空处理气体及其他气体。基板支撑件127设置在处理空间120中，该基板支撑件127设置在支撑轴杆124上，支撑轴杆124密封式延伸穿过腔室基座104，诸如在腔室基座104下方的区域中被波纹管(未示出)所围绕。支撑轴杆124耦接至控制器140，该控制器140控制电机以升高及降低支撑轴杆124(以及设置在该支撑轴杆124上的基板支撑件127)，以在基板115的处理期间支撑基板115，且将基板115移送到处理腔室100和从处理腔室100移送基板115。
基板115通过一个或多个侧壁102中的一个中的开口126装载到处理空间120中，常规上该开口126在基板115处理期间以门或阀(未示出)密封。在此，使用常规升降销系统(未示出)将基板115移送到基板支撑件127的表面以及从基板支撑件127的表面移送，该常规升降销系统包括穿过基板支撑件可移动地配置的多个升降销(未示出)。一般而言，多个升降销是通过升降销箍(未示出)从下方接触，并且该升降销移动而在基板支撑件127的表面上方延伸，从而将基板115从基板支撑件127上升起，且使机器人搬运器能够进出。当升降销箍(未示出)处于降低位置时，多个升降销的顶部定位成与基板支撑件127的表面齐平或在该表面下方，且基板安置于该基板支撑件127的表面上。该基板支撑件可在开口126下方的下部位置与升高位置之间移动，该下部位置用于将基板放置在该基板支撑件上或是从该基板支撑件移除基板115，而该升高位置用于基板115的处理。在一些实施例中，使用设置在基板支撑件中的电阻式加热组件129和/或一个或多个冷却通道137将基板支撑件127以及设置在该基板支撑件127上的基板115维持在期望的处理温度。一般而言，冷却通道137流体耦接至冷却剂源133，例如具有相对高电阻的修饰水源或是冷媒源。
在一些实施例中，处理腔室100进一步耦接至远程等离子体源107，该远程等离子体源107提供气态自由基至处理容积120。一般而言，远程等离子体源(RPS)包括电感耦合等离子体(ICP)源、电容耦合等离子体(CCP)源、或微波等离子体源。在一些实施例中，远程等离子体源是独立的RPS单元。在其他实施例中，远程等离子体源是与处理腔室100流体连通的第二处理腔室。在其他实施例中，远程等离子体源是在腔室盖103与喷头112之间的气室122中点燃并维持的远程等离子体128。在一些其他实施例中，从基于非等离子体的自由基源提供气态处理自由基至处理腔室，该基于非等离子体的自由基源为诸如：UV源，该UV源使用UV辐射将第一气体光解离成该气体的自由基物质；或是热丝源，诸如热丝CVD(HWCVD)腔室，该腔室使用热分解将第一气体解离成其自由基物质。
图2是使用气态自由基处理氮化硅层的方法的流程图。在活动210，方法200包括，将基板定位在基板支撑件上，该基板支撑件设置在处理腔室(诸如图1中描述的处理腔室)的处理容积中。在此，基板特征为氮化硅层，该氮化硅层已经沉积在该基板的表面上。
在一些实施例中，氮化硅层至少部分地设置在形成于基板表面中的多个开口中。在这些实施例中的一些实施例中，该多个开口的深宽比(深度对宽度的比)大于2:1，例如大于5:1、大于10:1、大于20:1、例如大于25:1。在一些实施例中，该开口的宽度小于约90nm，诸如小于约65nm、小于约45nm、小于约32nm、小于约22nm、例如小于约16nm，或是在约1nm与约90nm之间，诸如在约16nm与约90nm之间。
在一些实施例中，使用可流动化学气相沉积(FCVD)工艺沉积氮化硅层，例如聚硅氮烷层。在一些实施例中，在与用于氮化硅层的基于自由基的处理相同的处理腔室中执行该FCVD工艺。在一些实施例中，在与用于氮化硅层的基于自由基的处理的处理腔室不同的处理腔室中执行FCVD工艺。
一般而言，FCVD工艺包括：使一种或多种硅前驱物流入处理容积，将基板暴露于一种或多种硅前驱物，在该处理容积中提供一种或多种自由基共反应物，以及将基板暴露于该一种或多种自由基共反应物。在此，将基板暴露于一种或多种硅前驱物以及将基板暴露于一种或多种自由基共反应物为依序完成、同步完成、或以上述方式的组合完成。例如，在一些实施例中，将基板暴露于一种或多种硅前驱物的至少一部分与将基板暴露于一种或多种自由基共反应物的至少一部分重叠。
在一些实施例中，在将基板暴露于一种或多种硅前驱物和将基板暴露于一种或多种自由基共反应物之间净化处理容积。净化处理容积包括，使惰性气体流入处理容积以助于从该处理容积移除一些或所有的硅前驱物、自由基化的共反应物、以及处理气体副产物。一般而言，处理容积的压力期望地维持在约10毫托与约10托之间，诸如小于约6托、诸如小于约5托、或在约0.1托与约4托之间，诸如在约0.5托与约3托之间。在一些实施例中，基板期望地维持在约0℃至约400℃之间，或低于约200℃，诸如低于约150℃、低于约100℃，例如低于约75℃，或在约-10℃至约75℃之间，诸如约20℃至约75℃之间。
在一些实施例中，一种或多种硅前驱物包含硅烷化合物，例如硅烷(SiH4)、乙硅烷(Si2H6)、丙硅烷(Si3H8)、和丁硅烷(Si4H10)，或上述化合物的组合。在一些其他实施例中，该硅前驱物包含具有至少一个Si-N-Si官能基团的硅氮烷化合物，例如N,N’二甲硅烷基三硅氮烷(A)，诸如下文的硅氮烷化合物(A)-(E)的其他硅氮烷化合物(举例而言，下文中以(E)所示的三甲硅烷基胺(TSA))，或上述化合物的组合。在一些实施例中，该硅前驱物包含一种或多种硅烷化合物和一种或多种硅氮烷化合物的组合。在一些实施例中，硅前驱物实质上不含碳，其中实质上不含碳意味着该硅前驱物中不具有碳部分。
Figure BDA0002600939380000071
在一些实施例中，一种或多种自由基共反应物包括第二气体的自由基物质，诸如含氮的第二气体，例如NH3、N2、或上述气体的组合。例如，在一些实施例中，第二气体的自由基物质包括NH2、NH、N、和H自由基，或上述自由基的组合。在一些实施例中，第二气体实质上不含氧。在此，使用远程等离子体源(RPS)或通过电容耦合等离子体(CCP)将自由基共反应物提供至处理容积。
在一些实施例中，电容耦合等离子体由第二气体形成，第二气体在喷头与腔室盖之间的处理容积中被点燃并维持，诸如被点燃并维持在图1中描述的气室122中的远程等离子体128。一般而言，上文所述的FCVD工艺期望地提供可流动的氮化硅膜，使得能够实现自下而上填充形成在基板的表面中的高深宽比开口。例如，FCVD工艺可以用于填充宽度小于90nm并且深宽比大于约10:1的开口。在一些实施例中，该基板被维持在低于约200℃的温度。
在活动220，方法200包括将气态处理自由基提供至处理腔室的处理容积。在此，气态处理自由基包括第一气体的等离子体活化自由基物质，该第一气体选自由NH3、N2、H2、He、Ar或上述各项的组合所组成的群组。在一些实施例中，使用流体耦接至处理容积的远程等离子体源(RPS)(诸如图1中描述的远程等离子体源107)活化第一气体的分子以形成处理自由基。在其他实施例中，第一气体流进设置在喷头与腔室盖之间的气室，诸如图1中描述的气室122。在那些实施例中的一些中，处理自由基是通过下述方式形成：经由使第一气体电容耦合能量而点燃和维持该第一气体的远程等离子体(诸如远程等离子体128)。
在活动230，方法200包括将FCVD沉积的氮化硅层暴露于气态处理自由基，以形成经处理的氮化硅层。在一些实施例中，FCVD沉积氮化硅层和将所FCVD沉积的氮化硅层暴露于气态处理自由基在相同的处理腔室中完成。在那些实施例中的一些中，在沉积氮化硅层之后并且在将该氮化硅层暴露于气态处理自由基之前，使用惰性净化气体(诸如Ar、N2、或上述气体的组合)净化处理腔室的处理容积。净化处理容积从处理容积中移除一些或所有的未反应的硅前驱物、未反应的自由基化共反应物、和其它处理气体副产物。在其他实施例中，将所FCVD沉积的氮化硅层暴露于气态处理自由基是在与用于沉积氮化硅层的处理腔室(例如第一处理腔室)不同的处理腔室(在此，第二处理腔室)中完成。在那些其他实施例中的一些中，用于氮化硅层的基于自由基的处理的第二处理腔室和用于沉积氮化硅层的第一处理腔室通过移送腔室耦合。一般而言，移送腔室连续地维持在真空下，使得基板不会暴露于第一处理腔室和第二处理腔室之间的大气环境。
在一些实施例中，第二处理腔室是紫外线辐射(UV)腔室。在那些实施例中，用于形成处理自由基的第一气体流入处理腔室的处理容积并且暴露于来自UV辐射源的UV辐射，其中自由基前驱物对UV辐射的暴露提供使第一气体光解离成该气体的期望的处理自由基。一般而言，UV腔室维持在约10毫托和约500托之间的压力，并且基板维持在约0℃和约400℃之间。在一些实施例中，第二处理腔室包括多个加热组件，例如热丝CVD(HWCVD)腔室的加热灯丝。将加热组件维持在足以将第一气体热分解成其期望的处理自由基的温度。
在一些实施例中，方法200包括依序重复：沉积至少部分氮化硅层，随后对所至少部分沉积的氮化硅层进行基于自由基的处理，直到达到期望的氮化硅层厚度为止。一般而言，相较于将氮化硅层沉积到期望的厚度随后进行其基于自由基的处理，上述的依序重复有助于所得的经处理的氮化硅层的更均匀的致密化和化学计量。
本文所述方法的益处包括，相较于常规处理方法(例如将氮化物层暴露于高密度等离子体)，经处理的氮化硅有改善的致密化和化学计量。尽管不希望受任何特定理论所拘束，但据信由本文所述的方法所提供的NHx自由基与刚沉积的氮化硅层反应，而将N插入该氮化硅层的聚合物基质中，这改善了膜的化学计量，并且通过从聚合物膜移除H而进一步交联聚合物膜，导致其致密化。
尽管前述内容是针对本公开的实施例，但是可在不背离本公开的基本范围的情况下设计本公开的其他和进一步的实施例，并且本公开的范围由所附权利要求所决定。

Claims (15)

1.一种处理基板的方法，包括：
将基板定位在基板支撑件上，所述基板支撑件被设置在处理腔室的处理容积中；
处理已经沉积在所述基板上的氮化硅层，包括：
使第一气体的一种或多种自由基物质流动，所述第一气体包括NH3、N2、H2、He、Ar、或前述气体的组合；以及
将所述氮化硅层暴露于所述自由基物质。
2.如权利要求1所述的方法，其中，使所述第一气体的所述一种或多种自由基物质流动包括：
将所述第一气体流进所述处理腔室的所述处理容积；以及
通过使所述第一气体电容耦合能量，而形成所述第一气体的远程等离子体。
3.如权利要求1所述的方法，进一步包括将所述氮化硅层沉积于所述基板上，包括：
使一种或多种硅前驱物流进所述处理腔室的所述处理容积；
将所述基板暴露于所述一种或多种硅前驱物；
使包括第二气体的自由基物质的一种或多种自由基共反应物流动；以及
将所述基板暴露于所述一种或多种自由基共反应物。
4.如权利要求3所述的方法，其中使所述第二气体的所述一种或多种自由基物质流动包括：
使所述第二气体流进所述处理腔室的所述处理容积；以及
通过使所述第二气体电容耦合能量，而形成所述第二气体的远程等离子体。
5.如权利要求3所述的方法，其中所述一种或多种硅前驱物实质上不含碳。
6.如权利要求3所述的方法，其中所述一种或多种硅前驱物包括硅氮烷化合物。
7.如权利要求3所述的方法，其中所述第二气体的所述一种或多种自由基物质从远程等离子体源流至所述处理腔室的所述处理容积，所述远程等离子体源与所述处理容积流体连通。
8.如权利要求7所述的方法，进一步包括：在沉积所述氮化硅层之后以及在处理所沉积的氮化硅层之前，使用惰性净化气体净化所述处理容积，所述惰性净化气体流进所述处理容积中。
9.一种用于氮化硅层的基于自由基的处理的方法，包括：
将基板定位在基板支撑件上，所述基板支撑件被设置在处理腔室的处理容积中；以及
处理已经沉积在所述基板上的氮化硅层，包括：
使第一气体的一种或多种自由基物质流动，所述第一气体包括NH3、N2、H2、He、Ar、或前述气体的组合；以及
将所沉积的氮化硅层暴露于所述自由基物质，其中所述氮化硅层是使用一方法沉积，所述方法包括：
使一种或多种硅前驱物流进所述处理腔室的所述处理容积；
将所述基板暴露于所述一种或多种硅前驱物；
使包括第二气体的自由基物质的一种或多种自由基共反应物流动；以及
将所述基板暴露于所述一种或多种自由基共反应物。
10.如权利要求9所述的方法，其中所述第一气体的所述一种或多种自由基物质从远程等离子体源流至所述处理腔室的所说处理容积，所述远程等离子体源与所述处理容积流体连通。
11.如权利要求9所述的方法，其中所述第二气体的所述一种或多种自由基物质从远程等离子体源流至所述处理腔室的所述处理容积，所述远程等离子体源与所述处理容积流体连通。
12.如权利要求9所述的方法，其中使所述第一气体的所述一种或多种自由基物质流动包括：
将所述第一气体流进所述处理腔室的所述处理容积；以及
通过使所述第一气体电容耦合能量，而形成所述第一气体的远程等离子体。
13.一种形成氮化硅层的方法，包括：
在基板上沉积所述氮化硅层，包括：
使一种或多种硅前驱物流进第一处理腔室的处理容积；
将所述基板暴露于所述一种或多种硅前驱物；
使包括第一气体的自由基物质的一种或多种自由基共反应物流动；以及
将所述基板暴露于所述一种或多种自由基共反应物；以及
处理所述氮化硅层，包括：
使第二气体的一种或多种自由基物质流动，所述第二气体包括NH3、N2、H2、He、Ar、或前述气体的组合；以及
将所沉积的氮化硅层暴露于所述第二气体的所述自由基物质。
14.如权利要求13所述的方法，进一步包括：将所述基板从所述第一处理腔室移送到第二处理腔室，其中将所沉积的氮化硅层暴露于所述第二气体的所述自由基物质是在所述第二处理腔室中完成。
15.如权利要求13所述的方法，其中使所述第二气体的所述一中或多种自由基物质流动包括：使用UV辐射源将所述第二气体光解离成所述一种或多种自由基物质，所述UV辐射源设置在第二处理腔室中。
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