CN110235228B - 用于高深宽比结构的移除方法 - Google Patents

用于高深宽比结构的移除方法 Download PDF

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CN110235228B
CN110235228B CN201780069648.6A CN201780069648A CN110235228B CN 110235228 B CN110235228 B CN 110235228B CN 201780069648 A CN201780069648 A CN 201780069648A CN 110235228 B CN110235228 B CN 110235228B
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L·徐
陈智君
J·黄
王安川
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Abstract

示例性清洁或蚀刻方法可包括：使含氟前驱物流进半导体处理腔室的远程等离子体区域。方法可包括：在所述远程等离子体区域内形成等离子体，以生成所述含氟前驱物的等离子体流出物。所述方法还可包括：使所述等离子体流出物流进所述半导体处理腔室的处理区域。基板可定位在所述处理区域内，并且所述基板可包括被暴露的氧化物的区域。方法还可包括：将含氢前驱物提供至所述处理区域。所述方法可进一步包括：移除所述被暴露的氧化物的至少一部分，同时将所述处理区域内的相对湿度维持在低于约50％。在移除之后，所述方法可包括，将所述处理区域内的所述相对湿度增加至大于50％或为约50％。所述方法可进一步包括：移除额外量的所述被暴露的氧化物。

Description

用于高深宽比结构的移除方法
技术领域
本技术涉及半导体工艺与设备。更具体地说，本技术涉及清洁或蚀刻高深宽比结构。
背景技术
集成电路是通过在基板表面上产生复杂的图案化材料层的工艺而实现的。在基板上产生图案化的材料需要用于移除被暴露的材料的受控方法。化学蚀刻用在各种目的上，包括将光阻中的图案转移到下层的层、使层变薄或使已存在于表面上的特征的侧向尺寸变薄。通常，期望一种蚀刻一种材料蚀刻得比另一种材料要快的蚀刻工艺，这有助于例如图案转移工艺。此类蚀刻工艺被称作是对第一材料有选择性。材料、电路、和工艺的多样化的结果是，已开发对各种材料有选择性的蚀刻工艺。
蚀刻工艺可根据所述工艺中所用的材料而分为湿法或干法。湿法HF蚀刻相对于其他介电质和材料优先移除氧化硅。然而，湿法工艺可能难以贯穿某些受限的沟槽，且还可能有时会使剩余的材料变形。在基板处理区域内形成的原位等离子体中产生的干法蚀刻可贯穿更为受限的沟槽，且呈现出精细剩余结构的较少变形。然而，原位等离子体可能在所述原位等离子体放电时产生电弧而损坏基板。
因此，需要可用于产生高质量元件和结构的改进的系统和方法。本技术解决了这些和其他需求。
发明内容
示例性的清洁、移除、和蚀刻方法可包括：使含氟前驱物流进半导体处理腔室的远程等离子体区域。所述方法可包括：在所述远程等离子体区域内形成等离子体，以生成所述含氟前驱物的等离子体流出物。所述方法还可包括：使所述等等离子体流出物流进所述半导体处理腔室的处理区域。基板可定位在所述处理区域内，且所述基板可包括被暴露的氧化物的区域。所述方法还可包括：提供含氢前驱物至所述处理区域。所述方法可进一步包括：移除所述被暴露的氧化物的至少一部分，同时将所述处理区域内的相对湿度维持在低于约50％。在移除之后，所述方法可包括：将所述处理区域内的所述相对湿度增加至大于50％或为约50％。所述方法可进一步包括：移除额外量的所述被暴露的氧化物。
示例性方法还可包括：继续使所述等离子体流出物流进所述处理区域，同时增加所述处理区域内的相对湿度。可减少所述等离子体流出物的流速，同时增加所述处理区域内的相对湿度。在实施例中，可减少所述基板的温度，同时增加所述处理区域内的相对湿度。例如，所述温度可减少至少约5℃。在实施例中，可增加所述处理腔室内的压力，同时增加所述处理区域内的相对湿度。例如，所述压力可增加至少约1托。在一些实施例中，可将所述相对湿度增加至超过约65％。在已执行包括移除额外量的被暴露的氧化物的根据本技术的方法后，所述基板中氟浓度可低于5％或为约5％。类似地，所述基板中氧浓度可低于8％或为约8％。在一些实施例中，在将所述含氢前驱物提供至所述处理区域时，所述含氢前驱物可绕过所述远程等离子体区域。一些实施例中，所述处理区域于所述移除操作期间可维持无等离子体。此外，在示例性方法期间可递增地(incrementally)增加所述相对湿度，且可以以每增量小于20％或为约20％来递增地增加所述相对湿度。
本技术还涵盖清洁方法。所述方法可包括：使含氟前驱物流进半导体处理腔室的远程等离子体区域，同时在所述远程等离子体区域内形成等离子体，从而生成所述含氟前驱物的等离子体流出物。所述方法可包括：使所述等等离子体流出物流进所述半导体处理腔室的处理区域。所述处理区域可容纳或含有基板，所述基板可包括高深宽比特征，所述特征具有被暴露的氧化物的区域。在使所述等等离子体流出物流进所述处理区域的同时，所述方法可包括：提供含氢前驱物至所述处理区域。所述方法可进一步包括：移除所述被暴露的氧化物的至少一部分，同时将所述处理区域内的相对湿度维持在大于50％或为约50％。所述方法可进一步包括：在移除所述被暴露的氧化物的至少一部分之后，增加所述含氟前驱物的流速，同时将所述处理区域内的所述相对湿度维持在大于50％或为约50％。所述方法还可包括：移除额外量的所述被暴露的氧化物。
在实施例中，移除额外量的所述被暴露的氧化物可将氧的浓度降低至少约5％。在示例性方法中，所述含氟前驱物的流速可增加至少约2sccm。在实施例中，在移除操作前，氧化物的被暴露的区域的厚度可小于2nm或为约2nm。此外，在一些实施例中，所述高深宽比特征的临界尺寸可减少小于1％或减少约1％。
本技术还涵盖移除方法。所述方法可包括：使含氟前驱物流进半导体处理腔室的远程等离子体区域，同时在所述远程等离子体区域内形成等离子体，从而生成所述含氟前驱物的等离子体流出物。所述方法可包括：使所述等离子体流出物流进所述半导体处理腔室的处理区域。所述处理区域可容纳基板，所述基板可具有一个或多个高深宽比特征，所述一个或多个高深宽比特征具有被暴露的氧化物的区域。在使所述等离子体流出物流进所述处理区域的同时，所述方法可包括：将含氢前驱物提供至所述处理区域。所述方法可包括：继续使所述等离子体流出物和所述含氢前驱物流进所述处理区域达至少约200秒。所述方法还可包括：移除所述被暴露的氧化物的至少一部分，同时将所述处理区域内的相对湿度维持在大于50％或为约50％。在一些实施例中，所述移除操作可将所述基板内的氧的表面水平(surface-level)浓度减少至少约3％。
此技术可提供胜于常规系统和技术的许多优点。例如，所述工艺可允许高深宽比特征被蚀刻而不产生图案崩塌。此外，所述工艺可以在限制基板的表面污染水平的同时允许执行材料移除。结合下文的叙述和附图更详细地描述这些和其他实施例以及许多它们的优点和特征。
附图简单说明
通过参考说明书的其余部分以及附图，可进一步理解所公开的技术的本质与优点。
图1示出了根据本技术的实施例的示例性处理系统的一个实施例的俯视平面图。
图2A示出了根据本技术的实施例的示例性处理腔室的示意性截面图。
图2B示出了根据本技术的实施例的在图2A中所示的处理腔室的一部分的详细视图。
图3示出了根据本技术的实施例的示例性喷头的仰视平面图。
图4示出了根据本技术的实施例的方法中的示例性操作。
图5A至图5C示出了根据本技术的实施例的正被处理的基板的截面图。
图6示出了根据本技术的实施例的说明与相对湿度相关的元素的表面浓度的图表。
图7示出了根据本技术的实施例的方法中的示例性操作。
图8示出了根据本技术的实施例的说明与前驱物流速相关的元素的表面浓度的图表。
图9示出了根据本技术的实施例的方法中的示例性操作。
图10示出了本技术的实施例的说明与所经过的时间相关的元素的表面浓度的图表。
所述附图中的多个附图被包括作为示意图。应理解，附图只是为了说明，而非视为等比例，除非特定陈述所述附图为等比例。此外，作为示意图，所述附图供以帮助理解，并且可不包括相比于实际表示的所有方面或信息，并且为了说明的目的可包括额外或夸张的材料。
附图中，类似的部件和/或特征可具有相同的附图标记。进一步地，相同类型的各种部件可由下述方式区别：附图标记后跟随着区分类似部件的字母。若在说明书中仅使用第一附图标记，则描述适用于具有相同第一元件符号的类似部件中的任何一个，而不管字母如何。
具体实施方式
经稀释的酸可用在许多不同的半导体工艺中，以清洁基板并从这些基板移除材料。例如，经稀释的氢氟酸可以是针对氧化硅的有效蚀刻剂，并且可用于从硅表面移除氧化硅。在完成蚀刻或清洁操作后，可从晶片或基板表面干燥所述酸。使用经稀释的氢氟酸(“DHF”)可称为“湿法”蚀刻，并且所述稀释剂通常是水。水具有相对高的表面张力，所述表面张力可作用在与水接触的表面上。
在尺寸上持续缩小的元件图案化和特征可包括在基板上蚀刻或形成的精细特征。例如，许多处理操作可影响或形成基板中的沟槽、孔、或其他特征、或是基板上的材料。深宽比被定义为高度对宽度的比，所述深宽比在器件中可能是非常高的，并且可在5、10、20、50、100或更大的量级上。这些特征中的许多特征可不仅具有高深宽比而且还具有在几个纳米的尺度上的被缩小的尺寸，例如以使得基板上的临界尺寸——通常是这些特征的宽度或尺寸——可以是小于10nm、小于5nm、小于3nm、小于2nm、小于1nm、或甚至更小。例如，两个沟槽之间的任何特定的柱或壁的宽度可为仅几个纳米。此材料越薄，则施加在结构整体上的冲击应力越大。此外，构成所述结构的材料(若所述材料是基板材料、介电质、光阻等)还可能影响在材料上所施加的压力或应力的效果。
当精细的、高深宽比的特征被清洁、蚀刻、或处理时可能出现问题，因为流体可能呈现远远高于所述特征所能应付的表面张力的表面张力。在具有多个特征、层、或材料的设计中，甚至是少量的特征变形或崩塌都可能引发通过所生产的元件的短路，所述短路导致所述元件无法运作。例如，尽管当DHF用作为高深宽比特征上的蚀刻剂时DHF可在低深宽比结构上良好工作，但是当蚀刻操作结束并且干燥或移除DHF时，在干燥期间施加在特征上的表面张力可能引发图案崩塌。随着元件特征持续缩小，由于湿法蚀刻对高深宽比特征的影响，所述湿法蚀刻可能不再足够。用于在清洁操作中移除流体的一种有前景的技术是通过用超临界流体进行干燥操作。尽管这些技术可提供更干燥的且不太容易图案崩塌的表面，但制备量、硬件要求、以及所涉及的操作数量可能减少整体基板处理的效率。
本技术通过执行干法蚀刻工艺来克服这些问题，所述干法蚀刻工艺提供适当的选择性以用于相对于硅来移除氧化硅，同时维持高深宽比结构。所述技术利用等离子体增强前驱物(所述等离子体增强前驱物可包括含氟前驱物)以从硅表面移除氧化硅的暴露区域。通过利用非流体材料，可将对基板特征的影响最小化。针对蚀刻的术语“干”可用于意指液态水可不用于所述操作中，而与湿法蚀刻(在湿法蚀刻中水可用作诸如DHF之类的稀释剂或成分)不同。
尽管其余的公开内容例行地标识利用所公开的技术的特定蚀刻工艺，但容易理解的是所述系统和方法同样适用于可以在所述的腔室中发生的沉积和清洁工艺。因此，不应将本技术视为限制成单独地与蚀刻工艺或腔室使用。此外，尽管将示例性腔室描述为提供本技术的基础，但应理解本技术可应用于几乎任何可允许所述操作的半导体处理腔室。
图1示出了根据实施例的沉积、蚀刻、烘烤、和固化腔室的处理系统100的一个实施例的俯视平面图。在图中，一对前开式标准仓(FOUP)102供应各种尺寸的基板，所述基板由自动机械臂104接收并放置到低压保持区域106中，之后将所述基板放置到基板处理腔室108a-f之一，所述基板处理腔室108a-f定位在级联部分109a-c中。第二机械臂110可用于将基板晶片从保持区域106传输到基板处理腔室108a-f和往回输送。每一个基板处理腔室108a-f可装配成执行数个基板处理操作，所述数个基板处理操作包括本文所述的干法蚀刻工艺，此外还有循环层沉积(CLD)、原子层沉积(ALD)、化学气相沉积(CVD)、物理气相沉积(PVD)、蚀刻、预清洁、脱气、取向、和其他基板工艺。
基板处理腔室108a-f可包括一个或多个系统部件用于沉积、退火、固化、和/或蚀刻基板晶片上的介电膜。在一个配置中，两对处理腔室(例如108c-d和108e-f)可用于在基板上沉积介电材料，并且第三对处理腔室(例如108a-b)可用于蚀刻所沉积的介电质。在另一个配置中，所有三对腔室(例如108a-f)可配置成蚀刻基板上的介电膜。所述工艺中的任何一个或多个工艺可在与不同实施例中所示的制造系统分开的(一个或多个)腔室中进行。将理解，系统100构想了用于介电膜的沉积腔室、蚀刻腔室、退火腔室、和固化腔室的额外配置。
图2A示出了示例性工艺腔室系统200的截面图，在示例性工艺腔室200内有分隔的等离子体产生区域。在膜蚀刻(例如，氮化钛、氮化钽、钨、硅、多晶硅、氧化硅、氮化硅、氮氧化硅、碳氧化硅等)期间，工艺气体可穿过气体入口组件205流进第一等离子体区域215。可任选地将远程等离子体系统(RPS)201包括在系统中，并且所述远程等离子体系统201可对随后行进穿过气体入口组件205的第一气体进行处理。所述入口组件205可包括两个或多个不同的气体供应通道，其中第二通道(未图示)可绕过RPS 201(如果被包括的话)。
根据多个实施例，冷却板203、面板217、离子抑制件223、喷头225、以及基板支撑件265(基板支撑件265具有被配置在所述基板支撑件265上的基板255)被示出并其中的每个可被包括。底座265可具有热交换通道，热交换流体流动通过所述热交换通道以控制基板的温度，底座265可操作以在处理操作期间加热和/或冷却基板或晶片。还可利用嵌入式电阻加热器元件来电阻加热底座265的晶片支撑盘，以获得相对高的温度(所述温度诸如从高达100℃或为约100℃至超过1100℃或为约1100℃)，所述晶片支撑盘可包括铝、陶瓷、或上述材料的组合。
面板217可为金字塔形、锥形、或具有从窄的顶部部分扩张成宽的底部部分的另一种类似结构。另外面板217可如图所示那样地平坦并且包括用于分配工艺气体的多个贯穿通道。取决于RPS 201的用途，等离子体产生气体和/或被等离子体激发的物质可通过如图2B中所示的面板217中的多个孔以用于更均匀地传递至第一等离子体区域215中。
示例性配置可包括：使气体入口组件205通到气体供应区域258中，所述气体供应区域258由面板217与第一等离子体区域215隔开，使得气体/物质流过面板217中的孔进入第一等离子体区域215。可选择结构和操作性特征，以防止等离子体从第一等离子体区域215显著回流而回到供应区域258、气体入口组件205、和流体供应系统210中。面板217(或腔室的导电顶部部分)和喷头225被示出为具有位于特征之间的绝缘环220，其允许相对于喷头225和/或离子抑制件223来将AC电位施加至面板217。所述绝缘环220可定位在面板217与喷头225和/或离子抑制件223之间，使得电容耦合的等离子体(CCP)能够在第一等离子体区域中形成。另外，挡板(未图示)可位于第一等离子体区域215中，或不然则是与气体入口组件205耦接，以影响通过气体入口组件205进入区域的流体的流动。
离子抑制件223可包括板或其他几何形状，所述板或其他几何形状界定贯穿结构的多个孔径，所述孔径被配置成：抑制离子带电的物质迁移出第一等离子体区域215，同时允许未带电的中性或自由基物质通过所述离子抑制件223进入所述抑制件与所述喷头之间的活化气体输送区域。在实施例中，所述离子抑制件223可包括穿孔板(perforatedplate)，所述穿孔板具有各种孔径的配置。这些未带电的物质可包括高反应性物质，是用较低反应性的载气传输所述高反应性物质通过孔径。如上文所记叙，可减少离子物质通过所述孔的迁移，并且在一些实例中所述迁移可被完全地抑制。控制通过离子抑制件223的离子物质的量可有利地增加对与下方晶片基板形成接触的气体混合物的控制，这进而可增加对气体混合物的沉积特性和/或蚀刻特性的控制。例如，对气体混合物的离子浓度的调整可显著改变其蚀刻选择性，例如SiNx∶SiOx蚀刻比、Si∶SiOx蚀刻比等。在其中执行沉积的替代性实施例中，还能够针对介电材料改变共形对可流动(conformal-to-flowable)类型沉积的平衡。
离子抑制件223中的多个孔径可配置成控制活化气体(即离子物质、自由基物质、和/或中性物质)通过离子抑制件223。例如，可控制所述孔的深宽比(或孔直径比长度)和/或所述孔的几何形状使得减少活化气体中通过离子抑制件223的离子带电物质的流动。离子抑制件223中的孔可包括锥形部分以及圆柱形部分，所述锥形部分面向等离子体激发区域215，所述圆柱形部分面向喷头225。所述圆柱形部分的形状和尺寸可被设计成控制离子物质通向喷头225的流动。也可将可调整的电偏压施加至离子抑制件223来作为控制通过抑制件的离子物质的流动的额外手段。
离子抑制件223可充当减少或消除从等离子体产生区域行进至基板的离子带电物质的量。未带电的中性和自由基物质仍可通过离子抑制件中的开口而与基板反应。应注意，在实施例中，可不执行完全消除环绕基板的反应区域中的离子带电物质。在某些实例中，希望离子物质抵达基板，以执行蚀刻和/或沉积工艺。在这些实例中，所述离子抑制件可有助于将反应区域中的离子物质的浓度控制在有助于工艺的水平。
喷头225结合离子抑制件223可允许等离子体存在于第一等离子体区域215中，以避免在基板处理区域233中直接激发气体，同时仍使受激发的物质从腔室等离子体区域215行进至基板处理区域233中。以此方式，所述腔室可配置成防止等离子体接触被蚀刻的基板255。此举可有利地保护基板上图案化的各种复杂的结构和膜，若所述结构和膜直接接触所产生的等离子体则可能受到损坏、移位、或否则是翘曲。此外，当允许等离子体接触基板或抵达基板水平时，氧化物物质蚀刻的速率可能增加。因此，若材料的被暴露的区域是氧化物，则此材料可能通过维持等离子体远离所述基板而进一步被保护。
所述处理系统可进一步包括电源240，所述电源240电耦接所述处理腔室，以将功率提供至面板217、离子抑制件223、喷头225、和/或底座265，以在第一等离子体区域215或处理区域233中产生等离子体。取决于所执行的工艺，所述电源可配置成将可调整的量的功率输送至腔室。此类配置可允许可调的等离子体用在正被执行的工艺中。不同于远程等离子体单元(所述远程等离子体单元经常具有开或关的功能性)，可调的等离子体可配置成将特定量的功率递送给等离子体区域215。这进而可允许产生特定的等离子体特性，使得前驱物可以以特定方式解离，以增强这些前驱物所产生的蚀刻分布(etching profile)。
可在喷头225上方的腔室等离子体区域215中或是在喷头225下方的基板处理区域233中点燃等离子体。等离子体可存在于腔室等离子体区域215中，以从诸如含氟前驱物或其他前驱物之类的流入物产生自由基前驱物。可将通常在射频(RF)范围内的AC电压施加在处理腔室的导电顶部部分(诸如面板217)与喷头225和/或离子抑制件223之间，以在沉积期间在腔室等离子体区域215中点燃等离子体。RF电源可生成13.56MHz的高RF频率，但也可单独生成其他频率或结合13.56MHz的频率生成其他频率。
图2B示出影响通过面板217的处理气体分布的特征的详细视图253。如图2A和图2B中所示，面板217、冷却板203、和气体入口组件205交错而界定气体供应区域258，工艺气体可从气体入口205输送至所述气体供应区域258。所述气体可填充气体供应区域258并通过面板217中的孔径259流至第一等离子体区域215。孔径259可配置成以基本上单一方向的方式来引导流动，使得工艺气体可流进处理区域233，但可部分地或完全地防止工艺处理气体在横越面板217之后回流至气体供应区域258。
诸如喷头225之类的用在处理腔室部分200中的气体分配组件可称作双通道喷头(DCSH)，并且于图3中所描述的实施例中进行另外的详细描述。双通道喷头可提供蚀刻工艺，所述蚀刻工艺允许在处理区域233外分离蚀刻剂，从而提供所述蚀刻剂在被输送至处理区域中之前彼此之间和与腔室部件之间的交互作用受到限制。
喷头225可包括上板214以及下板216。所述板可彼此耦接，从而在所述板之间界定容积218。耦接这些板可以是为了提供穿过上板和下板的第一流体通道219以及穿过下板216的第二流体通道221。所形成的通道可配置成提供单独经由第二流体通道221从容积218通过下板216的流体进出，并且第一流体通道219可与在所述板与第二流体通道221之间的容积218流体隔离。可穿过气体分配组件225的一侧流体进出所述容积218。
图3是根据实施例的与处理腔室一并使用的喷头325的仰视图。喷头325可对应图2A图中所示的喷头225。贯穿孔365(示出第一流体通道219的视角)可具有多种形状和配置，以控制并影响穿过喷头225的前驱物的流动。小孔375(示出第二流体通道221的视角)可基本上均匀分布在喷头表面之上，甚至是分布在贯穿孔365之间，并且相较于其他组装型态可有助于在前驱物离开喷头时提供更为均匀的前驱物混合。
上文论述的腔室可用在执行包括了蚀刻方法的示例性方法。转至图4，图4示出根据本技术的实施例的方法400的示例性操作。在所述方法的第一操作之前，可以以一种或多种方式处理基板，之后再将所述基板放置在腔室的处理区域内，在所述处理区域中可执行方法400。例如，沟槽、孔、或其他特征可形成在基板中，所述基板可以包括硅基板。在一些实施例中，孔可由反应性离子蚀刻来形成，所述反应性离子蚀刻可利用氧化物硬掩模。反应性离子蚀刻可产生深的高深宽比结构，但可能在所形成的结构内留下残余物，所述残余物可能包括碳、氧、或其他材料。可执行灰化操作，虽然氧化物残余材料可能仍留在所形成的结构中。这些操作中的一些或全部可在先前描述的腔室或系统工具中执行，或可在相同的系统工具上的不同腔室中执行，所述系统工具可包括其中执行方法400的操作的腔室。
方法400可包括：在操作405处，将含氟前驱物流进半导体处理腔室的远程等离子体区域中。示例性腔室可为先前描述的腔室200，所述腔室200可包括RPS单元201或第一等离子体区域215中的一者或两者。这些区域中的任何一个或两个可以是用在操作405中的远程等离子体区域。在操作410处，等离子体可在所述远程等离子体区域内生成，其可生成含氟前驱物的等离子体流出物。在操作415处，所述等离子体流出物可流至腔室的处理区域。所述等离子体流出物可在处理区域中与基板相互作用，所述基板可包括形成为穿过半导体基板的沟槽或其他特征，所述半导体基板可包括硅、锗、或任何其他基板或可理解的元素的组合。
所述基板可包括被暴露的氧的区域，所述被暴露的氧可来自一个或多个源。例如，所述氧可为在已形成沟槽或其他特征之后留下来的氧硬掩模。所述氧化物还可为已由基板暴露至空气而形成的氧化物的层或包括所述氧化物的层。例如，当基板暴露至空气或某些其他氧源时，氧化物薄层可于基板上形成。在操作420处，可将含氢前驱物连同等离子体流出物提供至处理区域。在操作425处，所述等离子体流出物和含氢前驱物可与被暴露的氧化物相互作用以移除被暴露的氧化物的至少一部分。在移除期间，处理区域内的相对湿度可维持在低于50％或为约50％。
在已于操作425处移除所述氧化物的一部分之后，在操作430处，处理区域内的相对湿度可增加至大于50％或为约50％。在一些实施例中，在增加相对湿度的同时，所述等离子体流出物可继续流进处理区域中。随后可在操作435处移除额外量的被暴露的氧化物。通过在移除期间增加处理区域内的相对湿度，可移除额外量的氧化物，这可允许所述工艺有额外的益处，所述益处在下文中进一步描述。
用在所述方法中的前驱物可包括含氟前驱物或含氢前驱物。示例性含氟前驱物可为三氟化氮(NF3)，所述三氟化氮可流进远程等离子体区域中，所述远程等离子体区域可与处理区域分开但与处理区域流体耦接。可结合三氟化氮使用氟的其他源，或用氟的其他源取代三氟化氮。通常，含氟前驱物可流进远程等离子体区域，并且所述含氟前驱物可包括至少一种前驱物，所述前驱物选自由下述项构成的群组：原子氟、双原子氟、三氟化氮、四氟化碳、氟化氢、二氟化氙、和各种其他用于半导体处理或可用于半导体处理的含氟前驱物。所述前驱物还可包括任何数目的载气，所述载气可包括氮气、氦气、氩气、或其他稀有、惰性、或有用的前驱物。
所述含氢前驱物可包括氢、碳氢化合物、水、过氧化氢、或本领域技术人员理解的可包括氢的其他材料。还可与第二前驱物一起包括诸如载气或惰性材料之类的额外前驱物。所述前驱物中的一个或多个可绕过远程等离子体区域并且流进处理腔室的额外区域。这些前驱物可在处理区域或腔室的某些其他区域中与等离子体流出物混合。例如，当含氟前驱物流过远程等离子体区域以产生含氟等离子体流出物时，所述含氢前驱物可绕过远程等离子体区域。所述含氢前驱物可通过腔室顶部的旁路(bypass)绕过远程等离子体区域，或是可诸如通过提供进出喷头内的容积的端口流进腔室的分开的区域，所述喷头诸如为图2的喷头225。含氢前驱物可随后流进处理区域，在所述处理区域处所述前驱物可随后与含氟等离子体流出物混合或相互作用。在实施例中，在移除操作期间所述等离子体处理区域可维持无等离子体。无等离子体意指在操作期间在处理区域内可不主动地形成等离子体，然而在所述操作期间可使用如先前所述的远程产生的等离子体流出物。
可参考图5A至图5C来进一步理解本技术的额外方面。图5示出根据本技术的实施例的被处理的基板的截面图。以图5A开始，示出其上可利用本技术的基板的截面图。例如，硅基板505可具有形成或界定于其表面内的一个或多个特征，诸如所示出的沟槽510。在本技术所涵盖的实施例中，沟槽510可由反应性离子蚀刻工艺形成，然而类似地也涵盖可形成沟槽与其他特征的其他的蚀刻工艺。沟槽510可为如先前所论述的高深宽比沟槽，且所述沟槽510的深宽比可为大于10、大于50、大于100、或在这些数值中的任何数值内或如可形成更深、更窄的沟槽的其他数值。
在其中已使用反应性离子蚀刻而形成沟槽510的示例性情况中，氧化物硬掩模515可形成于基板505的表面上。此外，残余材料520可形成于沟槽510内或留在所述沟槽510内，所述残余材料520可包括碳、氧、或来自蚀刻的其他杂质。可执行工艺的操作(诸如上文所述的工艺400的所选操作)以从硅基板505的表面移除被暴露的氧化物材料。例如，可将含氟前驱物的等离子体流出物以及含氢前驱物输送至处理区域，以至少部分地移除氧化物硬掩模515以及残余材料520。因为沟槽510以及任何其他特征可具有高深宽比，所以在多个实施例中可将处理区域内的相对湿度维持在低于约50％。通过将相对湿度维持在低于约50％，水滴可不沿着表面形成，所述水滴在被干燥或移除时可能会引发图案变形或崩塌。
在已移除氧化物硬掩模515以及残余材料520之后，可能会留下氧化物薄膜。如图5B中所示，氧化物材料525可存在于基板505上。例如，氧化物材料525可以是因暴露于空气而遍及硅表面存在的氧化物层，或者可以是氧化物硬掩模515的剩余部分。氧化物材料525可以是为氧化物薄层，所述氧化物薄层可小于10nm或为约10nm、小于8nm或为约8nm、小于6nm或为约6nm、小于5nm或为约5nm、小于4nm或为约4nm、小于3nm或为约3nm、小于2nm或为约2nm、小于1nm或为约1nm、或更小。诸如关于图4论述的干法蚀刻操作可能难以移除氧化物材料525。例如，剩余的氧化物材料525可能在硅基板505与上层的氧化物材料525之间的界面处稍微较非晶形。在硅基体与氧化硅结构之间可能共享最终的氧原子层。一些情况中，干法蚀刻操作可能无法劈裂这些接合，这可能允许残余的氧留在表面处，诸如具有氧化物材料525。
可包括关于图4所述的某些操作的干法蚀刻操作可增加基板表面水平处的氟浓度。当干法蚀刻无法从硅表面劈裂最终的氧层时，用于蚀刻剂中的氟可接合或连结所述氧化物材料525。湿法蚀刻在用于较低深宽比特征时可不在基板内保留如干法蚀刻那样的氟的量，但湿法蚀刻可能无法维持高深宽比特征，并且可能由于表面张力而引发图案崩塌。残余的氟可作为影响器件功能的杂质。例如，沟槽或特征可能例如在存储器器件的制造中形成。在所述单元形成前，可能寻求相对地或基本上纯净的基板表面。杂质可能增加来自器件的漏电流，这可能进而增加功率消耗，并由于增加刷新速率以维持存储器数据免于遗漏而造成电池寿命减少。
氧化物材料525可使基板内的表面水平浓度的氟增加。附接至氧化物材料525或所述氧化物525内所含的氟在所述基板的某些区域(诸如中央区域)可多达或大于8原子％。例如，用于将由于此杂质造成的漏电流减至最少的期望的氟水平可为低于3％或为约3％。这样的水平的氟结合可通过湿法蚀刻来产生，但当特征尺寸减少时，湿法蚀刻可能引发图案崩塌以及器件失效。但本技术可利用相对湿度和/或一个或多个其他条件(下文中论述)来将氟的表面水平浓度减少至低于其他干法蚀刻工艺。
如上文针对图4所述，可将处理腔室内的相对湿度增加至超过约50％。通过增加相对湿度，可从硅表面移除额外的氧材料，这可移除可能与氧相关的残余的氟。通过减少氟的原子百分比，可减少漏电流，且可改进器件性能。然而，发明人已另外确定，可以以一系列的操作来执行所述操作，所述一系列的操作先移除氧化物材料的体部分(bulk portion)，之后增加相对湿度。如果一开始将相对湿度增加至超过50％，则可能发生某些问题。在足够高的相对湿度下，水滴可能形成在基板表面上，这随后可如上文所解释的那样引发图案崩塌或变形。甚至是单层的液态水都已显示出会产生图案变形或崩塌。
此外，在用干法蚀刻剂移除期间的氧化物硬掩模可能产生氟化硅。然而，利用水，可从所述氧化物硬掩模产生氟硅酸，这可能由于相对发粘的稠度而引发图案崩塌。因此，当正在移除氧化物硬掩模时，可在较低的相对湿度(例如，诸如约25％的相对湿度)下执行所述操作，以移除硬掩模材料的主要部分。在其他实施例中，可将所述相对湿度维持在低于50％或约50％、低于45％或约45％、低于40％或约40％、低于35％或约35％、低于30％或约30％、低于25％或约25％、低于20％或约20％、低于15％或约15％、低于10％或约10％、或更低。所述相对湿度还可维持在这些数值中的任何数值之间，或维持在被包括在这些范围内的任何更小的范围。
当已充分减少剩余氧化物材料(诸如减少至低于几纳米或更低的阈值)时，或是当蚀刻操作可能不移除额外氧化物材料时，可将相对湿度增加至超过约50％。增加的相对湿度可允许额外氧被移除，且允许可与所述氧化物相关联或附接的氟也被移除。在实施例中，可将所述相对湿度增加至超过50％或约50％，并还可将所述相对湿度增加至超过55％或约55％、超过60％或约60％、超过65％或约65％、超过70％或约70％、超过75％或约75％、超过80％或约80％、超过85％或约85％、超过90％或约90％、超过95％或约95％、或更高，然而在100％的相对湿度下可能存在液态水，这可能引发图案崩塌或变形。因此，所述相对湿度可维持在低于100％或为约100％、在其余所述的百分比中的任何百分比之间、或是在所述的范围内的任何较小的范围内。
如图5C中所示，所增加的相对湿度可允许额外氧化物材料525被从基板505移除，这可允许所结合的氟被移除。本技术可类似地用于移除可能存在于基板上的氧薄层或氧化物薄层(诸如因暴露空气所产生的氧薄层或氧化物薄层)，而不需要用于移除所述硬掩模材料的操作。例如，可能已暴露至空气的基本上干净的基板可具有为了在额外处理之前进一步清洁所述基板所执行的方法400的某些操作，诸如以与图5B中所示的基板类似的基板来开始。
转至图6，图6示出根据本技术的实施例的说明与相对湿度相关的元素的表面浓度的图表。所述图表示出以不断增加的湿度来执行的方法400的所选操作。例如，基板(诸如硅基板)可具有氧化物材料的薄层，诸如图5B中所示的层525。含氢前驱物(诸如水蒸气)可与含氟前驱物的等离子体流出物一起被输送至半导体处理腔室的处理区域。图6示出菱形605，所述菱形605对应于硅基板内(诸如在基板表面处的残余氧化物材料内)的氟的浓度。图6还包括矩形610，所述矩形610对应于硅基板内(诸如在表面水平氧化物材料处)的氧的浓度。如图6中所示，移除操作可不完全移除氧化物材料。三角形615示出基板表面上的残余氧化物材料的真实厚度。如所示，所述厚度在硬掩模移除后可小于1nm，诸如约
Figure BDA0002055471520000151
图6还示出随着相对湿度增加至超过25％，所述氟浓度稍微减少，同时氧浓度以及氧化物厚度基本上维持。然而，随着相对湿度增加至超过约50％的相对湿度，发生逐步的改变，且氧浓度、氧化物厚度、以及氟浓度都减少。氟浓度可减少至低于约2％，这可提供充足的器件质量以及泄漏效应。因此，图6示出本技术如何利用增加的相对湿度来减少基板内的氟浓度并且同时维持表面上的特征。用于产生图6的器件在基板上维持临界尺寸，例如高深宽比特征基本上并未减少且在基板上未发生图案变形以及崩塌。在实施例中，基板的临界尺寸(诸如或包括高深宽比特征宽度)可在实施例中减少小于10％，且可减少小于8％或约8％、小于6％或约6％、小于5％或约5％、小于4％或约4％、小于3％或约3％、小于2％或约2％、小于1％或约1％、或可基本上或实质上由本技术所维持。
工艺的条件还可能影响方法400中执行的操作以及根据本技术的其他移除方法。在实施例中，方法400的操作中的每一个操作可在恒温期间执行，然而在一些实施例中，可在不同操作期间调整所述温度。例如，在实施例中，在方法400期间可将基板温度、底座温度、或腔室温度维持在低于50℃或约50℃。所述基板温度可维持在低于45℃或约45℃、低于40℃或约40℃、低于35℃或约35℃、低于30℃或约30℃、低于25℃或约25℃、低于20℃或约20℃、低于15℃或约15℃、低于10℃或约10℃、低于5℃或约5℃、低于0℃或约0℃、低于-5℃或约-5℃、或更低。然而，在一些实施例中，可将温度维持在超过0℃或约0℃以防止含氢前驱物(所述含氢前驱物可为水)冻结。所述温度还可维持在这些范围内的任何温度、这些范围所涵盖的较小范围、或在这些范围中的任何范围之间。
在一些实施例中，可在第一温度下执行第一移除操作425，并且可在第二温度下执行额外的移除操作435。所述温度中的任何一个或两个可在上述范围中的任何范围内。在实施例中，第二温度可以低于第一温度。例如，在相对湿度增加期间，基板温度可从第一温度降低至第二温度。通过降低基板温度，还可增加晶片水平处的相对湿度，而不添加基本上更多的水蒸气至处理腔室。随后可减少水滴在腔室部件上或在基板上形成的机会，这样可有助于减少或防止图案变形或崩塌。
例如，在实施例中，第一温度可大于10℃或为约10℃，并且第二温度可小于10℃或为约10℃。在一些实施例中，所述第一温度可在约10℃至约20℃之间、在约11℃至约18℃之间、在约12℃至约15℃之间、或在多个实施例中可为约12℃、约13℃、约14℃、或约15℃。此外，在实施例中，所述第二温度可在约0℃至约10℃之间、在约1℃至约8℃之间、在约2℃至约5℃之间、或在实施例中可为约2℃、约3℃、约4℃、或约5℃。第一温度与第二温度之间的温度减少量在实施例中可以是至少约2℃，并且可以是至少3℃或约3℃、至少4℃或约4℃、至少5℃或约5℃、至少6℃或约6℃、至少7℃或约7℃、至少8℃或约8℃、至少9℃或约9℃、至少10℃或约10℃、至少11℃或约11℃、至少12℃或约12℃、或更大。此外，温度减少量可以是小于15℃或约15℃、或在这些范围中的任何范围之间的或是在这些范围中的任何范围内的任何较小范围。
腔室内的压力也可影响所执行的操作，并且在实施例中所述腔室压力可维持在低于约50托、低于40托或约40托、低于30托或约30托、低于25托或约25托、低于20托或约20托、低于15托或约15托、低于10托或约10托、低于5托或约5托、低于1托或约1托、或更小。所述压力还可维持在这些范围内的任何压力、这些范围所涵盖的较小范围内、或这些范围中的任何范围之间。
在一些实施例中，可在第一压力下执行第一移除操作425，并且可在第二压力下执行额外的移除操作435。所述压力中的任何一个压力或两个压力可在上述的范围中的任何范围内。在实施例中，第二压力可高于第一压力。例如，在相对湿度增加期间，处理腔室内的压力可从第一压力增加至第二压力。通过增加腔室内的压力，还可增加晶片水平处的相对湿度，而不添加基本上更多的水蒸气至处理腔室。随后可减少水滴在腔室部件上或在基板上形成的机会，这又可有助于减少或防止图案变形或崩塌。
例如，在实施例中，第一压力可小于10托或为约10托，并且第二压力可大于10托或为约10托。在一些实施例中，第一压力可在约0托至约10托之间、在约3托至约9托之间、在约5托至约8托之间，或在实施例中可为约5托、约6托、约7托、或约8托。在实施例中，所述第二压力可在约10托至约20托之间、在约10托至约18托之间、在约11托至约15托之间，或在多个实施例中可为约11托、约12托、约13托、约14托、或约15托。在实施例中，第一压力与第二压力之间的压力增加量可为至少约1托，并且在实施例中可为至少2托或约2托、至少3托或约3托、至少4托或约4托、至少5托或约5托、至少6托或约6托、至少7托或约7托、至少8托或约8托、或更大。所述压力增加量在多个实施例中可小于10托或为约10托、或可以是在这些范围中的任何范围内的或是在这些范围中的任何范围之间的较小范围。
所述前驱物中的一个或多个前驱物的流速也可与其他处理条件一并调整。例如，可减少含氟前驱物的流速，同时增加处理区域内的相对湿度，然而在一些实施例中，可维持或增加所述流速。在方法400的操作中的的任何操作期间，所述含氟前驱物的流速可在约2sccm至约100sccm之间。此外，所述含氟前驱物的流速可以是至少2sccm或约2sccm、至少3sccm或约3sccm、至少4sccm或约4sccm、至少5sccm或约5sccm、至少6sccm或约6sccm、至少7sccm或约7sccm、至少8sccm或约8sccm、至少9sccm或约9sccm、至少10sccm或约10sccm、至少11sccm或约11sccm、至少12sccm或约12sccm、至少13sccm或约13sccm、至少14sccm或约14sccm、至少15sccm或约15sccm、至少16sccm或约16sccm、至少17sccm或约17sccm、至少18sccm或约18sccm、至少19sccm或约19sccm、至少20sccm或约20sccm、至少25sccm或约25sccm、至少30sccm或约30sccm、至少40sccm或约40sccm、至少50sccm或约50sccm、至少60sccm或约60sccm、至少80sccm或约80sccm、或更大。所述流速还可在这些所述流速中的任何所述流速之间，或可在这些数值中的任何数值所涵盖的较小范围内。
取决于所用的前驱物，可以使含氢前驱物以这些流速中的任何流速来流动，所述所用的前驱物可为任何数目的含氢前驱物。例如，若利用水蒸气，则水可以以至少1g/分钟或约1g/分钟的速率引入。所述水还可以以下述速率引入：至少2g/分钟或约2g/分种、至少3g/分钟或约3g/分钟、至少4g/分或约4g/分钟、至少5g/分钟或约5g/分钟、至少6g/分钟或约6g/分钟、至少7g/分钟或约7g/分钟、至少8g/分钟或约8g/分钟、至少9g/分钟或约9g/分钟、或更大，然而可以以低于约10g/分钟引入水，以减少部件以及基板上的水冷凝。可以以在这些所述流速中的任何流速之间、或是这些数值中的任何数值所涵盖的较小范围内的流速来引入水。
当完成方法400时，在实施例中，基板中的氟的浓度可为低于8％或约8％，并且可为低于7％或约7％、低于6％或约6％、低于5％或约5％、低于4％或约4％、低于3％或约3％、低于2％或约2％、低于1％或约1％、或更低。类似地，基板中的氧的浓度在多个实施例中可低于15％或约15％，并且在实施例中可为低于12％或约12％、低于10％或约10％、低于9％或约9％、低于8％或约8％、低于7％或约7％、低于6％或约6％、低于5％或约5％、低于4％或约4％、低于3％或约3％、低于2％或约2％、低于1％或约1％、或更低。
在一些实施例中，可以递增地(incrementally)执行相对湿度的增加。例如，在将前驱物输送至处理区域的同时，可将相对湿度增加特定百分比。可使相对湿度增加一个或多个增量(increment)增加相对湿度，所述一个或多个增量可为小于50％或约50％的相对湿度、小于40％或约40％的相对湿度、小于30％或约30％的相对湿度、小于20％或约20％的相对湿度、小于15％或约15％的相对湿度、小于10％或约10％的相对湿度、小于5％或约5％的相对湿度、或更小。还可以使所述相对湿度增加在这些数值中的任何数值之间或在这些范围中的任何数值所涵盖的较小范围内的增量。此外，在实施例中，可将相对湿度从起始的相对湿度逐渐增加至最终的相对湿度，此操作可执行一段时间以减少过剩的水凝结发生的机会，所述过剩的水凝结可能导致图案变形或崩塌。
转至图7，图7示出根据本技术的实施例的方法700中的示例性操作。方法700可包括先前所述的方法400的操作、条件、参数或结果中的一些或全部。例如，方法700可包括：在操作705处，将含氟前驱物流进半导体处理腔室的远程等离子体区域。可使所述前驱物流动并同时在所述远程等离子体区域内形成等离子体，以生成含氟前驱物的等离子体流出物。在操作710处，所述等离子体流出物可流入腔室的处理区域。基板可容纳在处理区域内，且所述基板可通过高深宽比特征来表征，所述高深宽比特征具有被暴露的氧化物的区域。
在操作715处，当所述等离子体流出物流进处理区域时，可以使含氢前驱物流进所述处理区域。在实施例中，所述含氢前驱物可绕过所述远程等离子体区域。在操作720处，可移除被暴露的氧化物的至少一部分，同时将所述处理区域内的相对湿度维持在大于50％或约50％。在操作725处，在至少局部的移除之后，可以增加含氟前驱物的流速，同时将所述处理区域内的相对湿度维持在大于50％或约50％。在操作730处，可移除额外的被暴露的氧化物。
本技术还可在其中相对湿度可能无法增加至超过阈值的情况中有效产生上文所述的益处。此外，结合相对湿度的增加，可增加含氟前驱物的流速，这样可进一步移除额外的氧或氟材料。所述方法可包括阈值相对湿度值，诸如至少约50％的相对湿度，以提供对上文所述的材料的移除。对残余的氧化物层而言，当相对湿度减少至低于50％或约50％时，接合可能会更难以劈裂或无法劈裂，如上文所论述。
图8示出根据本技术的实施例的说明与前驱物流速相关的元素的表面浓度的图表。所述图表示出在其中增加含氟前驱物的流速的本技术的操作期间硅基板中的氧和氟的结合的影响。操作期间的相对湿度维持在约50％至约65％之间。如所示，在增加含氟前驱物流速的同时将氟浓度维持在低于约3％的结合，如矩形805所示。随着流速增加，先前论述的氧化物层的厚度在厚度上减少超过1埃，如三角形815所示。此外，如菱形810所示的氧结合随着流速增加而减少。在增加之前以及增加之后的含氟前驱物的流速可以是先前论述的前驱物流速中的任何流速。在实施例中，所述流速可增加至至少1sccm或约1sccm、至少2sccm或约2sccm、至少3sccm或约3sccm、至少4sccm或约4sccm、至少5sccm或约5sccm、至少6sccm或约6sccm、至少7sccm或约7sccm、至少8sccm或约8sccm、至少9sccm或约9sccm、至少10sccm或约10sccm、至少11sccm或约11sccm、至少12sccm或约12sccm、至少13sccm或约13sccm、至少14sccm或约14sccm、至少15sccm或约15sccm、至少20sccm或约20sccm、或更高。
在实施例中，所述移除操作可将氧结合减少至低于约14％，且可将所述氧结合减少至低于12％或约12％、低于10％或约10％、低于7％或约7％、低于6％或约6％、低于5％或约5％、低于4％或约4％、低于3％或约3％、低于2％或约2％、或更低。所述移除操作还可将所述氧结合减少至少2％或约2％，且可将所述氧结合减少至少3％或约3％、至少4％或约4％、至少5％或约5％、至少6％或约6％、至少7％或约7％、至少8％或约8％、至少9％或约9％、至少10％或约10％、至少11％或约11％、至少12％或约12％、或更多。
可对氧化物材料执行方法700，所述氧化物材料诸如图5B中所示的氧化物材料525。在实施例中，氧化物的暴露区域可特征在于小于5nm或约5nm的厚度，且可特征在于下述厚度：小于4nm或约4nm、小于3nm或约3nm、小于2nm或约2nm、小于1nm或约1nm、小于
Figure BDA0002055471520000201
或约
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、小于
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或约
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、小于
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或约
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、小于
Figure BDA0002055471520000207
或约
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、小于
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或约
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、小于
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或约
Figure BDA00020554715200002012
、小于
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或约
Figure BDA00020554715200002014
、或更小。通过以由小于几纳米或约几纳米的厚度为特征的氧化物材料执行所述操作，可减少氟硅酸的影响，这可减少图案变形或崩塌。此外，方法700可维持或限制对基板特征尺寸或基板临界尺寸的影响，所述尺寸可减少小于5％或约5％、小于4％或约4％、小于3％或约3％、小于2％或约2％、小于1％或约1％，或所述尺寸可由所述方法基本上或实质上维持。
图9示出根据本技术的实施例的方法900中的示例性操作。方法900可包括先前所述的方法400或方法700中的操作、条件、参数、或结果中的一些或全部。可对上文针对方法700或方法400所论述的残余氧化物材料执行方法900。例如，方法900可包括：在操作905处，将含氟前驱物流进半导体处理腔室的远程等离子体区域。在操作910处，可使所述前驱物流动，同时在所述远程等离子体区域内形成等离子体，以生成含氟前驱物的等离子体流出物。在操作915处，可以使所述等离子体流出物流入腔室的处理区域中。基板可容纳在处理区域内，并且所述基板可特征在于高深宽比特征，所述高深宽比特征具有被暴露的氧化物的区域。
在操作920处，当所述等离子体流出物流进处理区域时，可将含氢前驱物流进所述处理区域。在实施例中，所述含氢前驱物可绕过所述远程等离子体区域。在操作925处，可连续地使所述前驱物流过处理区域达一段时间。在操作930处，在引入前驱物期间，可移除被暴露的氧化物材料的至少一部分。在移除期间，所述处理腔室内的相对湿度可以维持在大于50％或约50％(作为阈值)，如上文所述。
方法900还可在其中相对湿度可能无法增加至超过阈值的情况中有效产生上文所述的益处。此外，结合相对湿度的增加和/或含氟前驱物流速的增加，可在一段时间内执行氧化物材料的移除，以进一步减少基板处的氧浓度。
图10示出根据本技术的多个实施例的说明与经过的时间相关的元素的表面浓度的图表。将含氟等离子体流出物和含氢前驱物提供至图案化的基板达一段时间(如图所示，所述时间多达400秒)。将操作期间的相对湿度维持在约50％至约65％之间。如图所示，所述方法相对地维持氟浓度，同时减少基板中的氧浓度。氟结合由矩形1005所示，且氧结合由菱形1010所示。所述图表另外地用三角形1015来示出残余氧化物厚度的减少。如图所示，方法900的移除操作可将氧结合减少至少1％或约1％，且可减少氧结合至少2％或约2％、至少3％或约3％、至少4％或约4％、至少5％或约5％、至少6％或约6％、或更多。在实施例中，前驱物和等离子体流出物的输送可持续至少100秒或约100秒，且可持续至少150秒或约150秒、至少200秒或约200秒、至少250秒或约250秒、至少300秒或约300秒、至少350秒或约350秒、至少400秒或约400秒、至少450秒或约450秒、至少500秒或约500秒、或更长。然而，随着时间增加，可能会在基板中产生表面缺陷，且所述表面缺陷可能减少基板上的表面均匀度。因此，在一些实施例中，可执行所述操作达少于500秒或约500秒。
上文论述的方法可允许从基板移除氧化物材料，同时限制氟结合，并且同时维持基板特征的临界尺寸，所述基板特征可为高深宽比特征。如所论述，所执行的操作可包括下述项中的一个或多个：在移除期间增加相对湿度、在移除期间增加含氟前驱物流速、或继续所述移除达一段时间。还可调整额外的腔室操作，如本公开内容全文中所论述。通过利用本方法和操作，可清洁或蚀刻高深宽比特征，同时不引发图案崩塌(与湿法蚀刻不同)，且同时不增加或同时限制诸如氟之类的杂质引入(与一些常规的干法蚀刻不同)。
前文的描述中，为了解释的目的，已提出许多细节以提供对本技术地各种实施例的理解。然而，本领域技术人员会明了，可在没有这些细节中的一些细节或拥有额外的细节的情况下实践某些实施例。
已公开许多实施例，本领域技术人员会理解，可在不背离所述实施例的精神的情况下使用各种修改、替代结构、以及等效物。此外，并未描述许多已知的工艺和元件，以避免非必要地混淆本技术。因此，上文的叙述不应视为限制本技术的范围。此外，可将方法或工艺描述为依序或分步骤，但应理解，可同步执行这些操作，或以与所列出的顺序不同的顺序执行这些操作。
在提供值的范围的情况下，应理解除非上下文清楚地以其他方式规定，否则还特定公开了在所述范围的上限与下限之间的至下限的单位的最小分数的每一个中间值。还涵盖了在所陈述的范围中的任何所陈述的值或未陈述的中间值和在所述所陈述的范围中的任何其他所陈述的值或中间值之间的任何较窄范围。所述较小范围的上限与下限可独立地被包括在所述范围中或被排除在所述范围之外，并且其中极限中的的任何一个、无一个、或两个都被包括在所述较小范围中时的每一个范围也被涵盖在本技术内，但受所述所陈述的范围中的任何被特定排除的极限所限。当所陈述的范围包括所述限中的一个或两个时，还包括了排除所述所包括的极限中的任何一个或两个范围的范围。
如本文以及所附的权利要求中所使用的，单数形式的“一”、“一个”以及“所述”包括了多个参考，除非上下文以其他方式明确规定。因此，举例而言，对“一前驱物”的参考包括了多个此类前驱物，对“所述层”的参考包括对一个层或两个层的参考以及对于本领域技术人员来说已知的其等效物等。
同样，词语“包含”、“包括”、和“含有”在被用于此说明书以及下文的权利要求中时旨在指定了存在所陈述的特征、整体、部件、或操作，但其并不排除存在或添加一个或多个其他特征、整体、部件、操作、动作、或群组。

Claims (20)

1.一种蚀刻方法，包括：
将含氟前驱物流进半导体处理腔室的远程等离子体区域；
在所述远程等离子体区域内形成等离子体，以产生所述含氟前驱物的等离子体流出物；
使所述等离子体流出物流进所述半导体处理腔室的处理区域，其中所述处理区域容纳基板，所述基板包括被暴露的氧化物的区域；
将含氢前驱物提供至所述处理区域；
移除所述被暴露的氧化物的至少一部分，同时将所述处理区域内的相对湿度维持在低于50％；
在移除所述被暴露的氧化物的至少一部分之后，将所述处理区域内的所述相对湿度增加至大于50％或等于50％；以及
移除额外量的所述被暴露的氧化物。
2.如权利要求1所述的蚀刻方法，进一步包括：继续使所述等离子体流出物流进所述处理区域，同时增加所述处理区域内的所述相对湿度。
3.如权利要求2所述的蚀刻方法，其中在增加所述处理区域内的所述相对湿度的同时，减少所述等离子体流出物的流速。
4.如权利要求1所述的蚀刻方法，进一步包括：在增加所述处理区域内的所述相对湿度的同时，减少所述基板的温度。
5.如权利要求4所述的蚀刻方法，其中使所述温度减少至少5℃。
6.如权利要求1所述的蚀刻方法，进一步包括：在增加所述处理区域内的所述相对湿度的同时，增加所述处理腔室内的压力。
7.如权利要求6所述的蚀刻方法，其中将所述压力增加至少1托。
8.如权利要求1所述的蚀刻方法，其中将所述相对湿度增加至超过65％。
9.如权利要求1所述的蚀刻方法，其中在移除所述额外量的被暴露的氧化物之后，所述基板中的氟浓度低于5％或等于5％。
10.如权利要求1所述的蚀刻方法，其中在移除所述额外量的被暴露的氧化物之后，所述基板中的氧浓度低于8％或等于8％。
11.如权利要求1所述的蚀刻方法，其中所述含氢前驱物在被提供至所述处理区域时绕过所述远程等离子体区域。
12.如权利要求1所述的蚀刻方法，其中所述处理区域在所述移除操作期间维持无等离子体。
13.如权利要求1所述的蚀刻方法，其中以每增量低于20％或等于20％来递增地增加所述相对湿度。
14.一种清洁方法，包括：
使含氟前驱物流进半导体处理腔室的远程等离子体区域，同时在所述远程等离子体区域内形成等离子体，以产生所述含氟前驱物的等离子体流出物；
使所述等离子体流出物流进所述半导体处理腔室的处理区域，其中所述处理区域容纳基板，所述基板包括高深宽比特征，所述高深宽比特征具有被暴露的氧化物的区域；
在使所述等离子体流出物流进所述处理区域的同时，提供含氢前驱物至所述处理区域；
移除所述被暴露的氧化物的至少一部分，同时将所述处理区域内的相对湿度维持在大于50％或等于50％；
在移除所述被暴露的氧化物的至少一部分之后，增加所述含氟前驱物的流速，同时将所述处理区域内的所述相对湿度维持在大于50％或等于50％；以及
移除额外量的所述被暴露的氧化物。
15.如权利要求14所述的清洁方法，其中移除额外量的所述被暴露的氧化物将氧浓度降低至少5％。
16.如权利要求14所述的清洁方法，其中将所述含氟前驱物的流速增加至少2sccm。
17.如权利要求14所述的清洁方法，其中在所述移除操作前所述氧化物的暴露区域的厚度为小于2nm或等于2nm。
18.如权利要求14所述的清洁方法，其中将所述高深宽比特征的临界尺寸减少小于1％或等于1％。
19.一种移除方法，包括：
使含氟前驱物流进半导体处理腔室的远程等离子体区域，同时在所述远程等离子体区域内形成等离子体，以产生所述含氟前驱物的等离子体流出物；
使所述等离子体流出物流进所述半导体处理腔室的处理区域，其中所述处理区域容纳基板，所述基板包括高深宽比特征，所述高深宽比特征具有被暴露的氧化物的区域；
在使所述等离子体流出物流进所述处理区域的同时，提供含氢前驱物至所述处理区域；
继续使所述等离子体流出物和所述含氢前驱物流进所述处理区域达至少200秒；以及
移除所述被暴露的氧化物的至少一部分，同时将所述处理区域内的相对湿度维持在大于50％或等于50％。
20.如权利要求19所述的移除方法，其中所述移除操作将所述基板内的氧的浓度减少至少3％。
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