CN112567498A - 使用自组装单层的选择性沉积的方法 - Google Patents

使用自组装单层的选择性沉积的方法 Download PDF

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CN112567498A
CN112567498A CN201980053966.2A CN201980053966A CN112567498A CN 112567498 A CN112567498 A CN 112567498A CN 201980053966 A CN201980053966 A CN 201980053966A CN 112567498 A CN112567498 A CN 112567498A
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metal
metal surface
assembled monolayer
substrate
atop
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柯常
张闻宇
吴立其
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Applied Materials Inc
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Applied Materials Inc
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Abstract

公开了用于在具有金属表面和介电质表面的基板顶上选择性沉积层的方法和设备，包括：(a)使该金属表面接触一或多种金属卤化物、诸如金属氯化物或金属氟化物，以形成暴露的金属表面；(b)在该介电质表面顶上生长基于有机硅烷的自组装单层；及(c)在该基板的该暴露的金属表面顶上选择性地沉积层，其中该基于有机硅烷的自组装单层抑制该层在该介电质表面顶上的沉积。

Description

使用自组装单层的选择性沉积的方法
技术领域
本公开内容的实施方式一般涉及使用自组装单层选择性沉积的方法。
背景技术
选择性原子层沉积(ALD)和化学气相沉积(CVD)工艺能够有利地减少常规微影术中包含的步骤数目和成本，同时跟上器件尺寸缩小的步调。在后端产线(BEOL)应用中，以金属介电质图案选择性沉积有高度的潜在价值。已出现的一些替代性选择性基于硅的介电质沉积技术是模板控制式的生长、基于全息(holographic)的微影术、及类似技术。然而，由于在大气条件下与金属氧化物形成相关的限制之故，这些替代性技术中无一技术提供完整的解决方案。发明人已观察到，金属的本质引起了严峻的挑战，例如在金属表面上存在着原生氧化物。因为金属氧化物可作用如介电质，所以薄层的原生氧化物使得金属表面无法与用于自组装单层(SAM)的介电质表面区分，而导致选择性降低或是选择性损失。
因此，发明人已开发使用自组装单层作为牺牲层与成核抑制层的选择性介电质沉积的改良方法和设备。
发明内容
本文提供用于选择性沉积的方法和设备。在一些实施方式中，一种方法包括：在具有金属表面和介电质表面的基板顶上选择性地沉积层，包括：(a)使该金属表面接触一或多种金属卤化物，以形成暴露的金属表面；(b)在该介电质表面顶上生长基于有机硅烷的自组装单层；及(c)在该基板的该暴露的金属表面顶上选择性地沉积一层，其中该基于有机硅烷的自组装单层抑制该层在该介电质表面顶上的沉积。在多个实施方式中，该金属卤化物是金属氯化物、金属氟化物、碱金属氯化物、或上述卤化物的组合。
在另一实施方式中，提供一种调节具有金属表面和介电质表面的基板的方法，包括使该金属表面接触一种或多种金属卤化物，以形成暴露的金属表面，其中该暴露的金属表面抑制基于有机硅烷的自组装单层在该暴露的金属表面上的沉积。在多个实施方式中，该金属卤化物是金属氯化物、金属氟化物、碱金属氯化物、或上述卤化物的组合。
在一些实施方式中，一种方法包括：在具有金属表面和介电质表面的基板顶上选择性地沉积层，包括：(a)使该金属表面接触一种或多种金属氯化物、金属氟化物、或上述材料的组合，以形成暴露的金属表面；(b)在该介电质表面顶上生长基于有机硅烷的自组装单层；及(c)在该基板的该暴露的金属表面顶上选择性地沉积一层，其中该基于有机硅烷的自组装单层抑制该层在该介电质表面顶上的沉积。
在一些实施方式中，本公开内容涉及一种计算机可读媒体，在该计算机可读媒体上储存有数个指令，当执行这些指令时，这些指令引发处理腔室执行在具有金属表面和介电质表面的基板顶上选择性沉积层的方法，该方法包括：(a)使该金属表面接触一种或多种金属卤化物，以形成暴露的金属表面；(b)在该介电质表面顶上生长基于有机硅烷的自组装单层；及(c)在该基板的该暴露的金属表面顶上选择性地沉积一层，其中该基于有机硅烷的自组装单层抑制该层在该介电质表面顶上的沉积。
以下描述本公开内容的其他及进一步的实施方式。
附图说明
以上简要概述及以下更详细论述的本公开内容的实施方式可通过参照本公开内容的说明性实施方式来获得。然而，所附图式仅绘示本公开内容的典型实施方式，因此不应视为对本公开内容的范围的限制，因为本公开内容可容许其他等同有效的实施方式。
图1是根据本公开内容的一些实施方式的适合执行化学气相沉积工艺或原子层沉积工艺的处理腔室。
图2是根据本公开内容的一些实施方式的选择性沉积的方法的流程图。
图3A至图3E是根据本公开内容的一些实施方式的图2的处理序列的不同阶段期间的基板的说明性横截面视图。
图4是根据本公开内容的一些实施方式的调节具有金属表面和介电质表面的基板的方法的流程图。
为了助于了解，尽可能地使用了相同的附图标号来标示图式中共通的相同元件。这些图式并未按照比例绘制，并且可能为了清楚起见而简化。一个实施方式的元件和特征在没有进一步描述下可有利地并入其他实施方式。
具体实施方式
本文提供使用自组装单层(SAM)进行选择性沉积的方法。在一些实施方式中，本文所述的方法通过使金属表面接触一或多种金属卤化物、诸如金属氯化物、金属氟化物、及类似物，而形成暴露的金属表面，以有利地调节具有金属表面和介电质表面的基板，其中该暴露的金属表面抑制基于有机硅烷自组装单层在该暴露的金属表面上的沉积。暴露的金属表面有利地不包括有问题的氧化物层，该有问题的氧化物层可能会促进基于有机硅烷的自组装单层在该氧化物层上的沉积并且限制或破坏该工艺的选择性。
图2是根据本公开内容的一些实施方式的处理具有金属表面和介电质表面的基板的方法200的流程图。图3A至图3E是根据本公开内容的一些实施方式的在图2的工艺序列的不同阶段期间的基板的说明性横截面视图。本公开内容的方法可以在构造成用于原子层沉积(ALD)或化学气相沉积(CVD)的处理腔室中执行，例如下面与图1相关地讨论的处理腔室。
方法200在基板300上执行，如图3A所描绘，该基板300具有金属表面302及介电质表面304。在多个实施方式中，基板300可包括下述材料：诸如结晶硅(例如，Si<100>或Si<111>)、硅锗、掺杂或未掺杂的多晶硅、掺杂或未掺杂的硅晶片、图案化或非图案化的晶片、绝缘体上覆硅(SOI)、碳掺杂的氧化硅、氮化硅、掺杂硅、锗、砷化镓、玻璃、蓝宝石、及上述材料的组合。在实施方式中，基板300可具有各种尺寸，对于圆形基板而言，诸如200mm、300mm、450mm、或其他直径。基板300也可以是任何多边形、正方形、矩形、弯曲或其他非圆形工件，诸如用在制造平板显示器中的多边形玻璃基板。除非另有注记，否则本文所述的实施方式和实例在诸如基板300的基板上进行，该基板具有200mm直径、300mm直径、或450mm直径的基板。
在实施方式中，介电质表面304与金属表面302并不相同。在一些实施方式中，介电质表面304经由任何适合的原子层沉积工艺或化学层沉积工艺沉积。在一些实施方式中，介电质表面304可包括沉积在基板300顶上的低k介电质层。在一些实施方式中，介电质表面304可包括适合用于半导体器件制造的任何低k介电质材料。适合作为低k介电质材料的非限制性材料可包括含硅材料，例如氧化硅(SiO2)、氮化硅、或氮氧化硅(SiON)。在实施方式中，低k介电质材料可具有小于约3.9的低k值(例如，约2.5至约3.5)。在一些实施方式中，介电质表面304可包括氧化铪，诸如HfOx。
在一些实施方式中，经由任何适合的原子层沉积工艺或化学层沉积工艺沉积金属表面302。在一些实施方式中，该金属表面302可包括适合用于半导体器件制造的任何金属。适用于金属表面302的非限制性金属包括：铜(Cu)、钴(Co)、钨(W)、铌(Nb)、钌(Ru)、或钼(Mo)，以及诸如合金及类似物的上述金属的组合。参照图3A，示出金属氧化物层305设置在金属表面302顶上。金属氧化物层305可以是原生氧化物层或形式，这是因为金属表面302接触例如在空气或水中的氧。金属氧化物层305是有问题的，原因在于，金属氧化物层305充当介电层或是会促进基于有机硅烷的自组装单层在该金属氧化物层上的沉积。在金属氧化物层305和金属表面302顶上形成基于有机硅烷的自组装单层可以抑制或减少选择性沉积方法的选择性。在多个实施方式中，在沉积自组装单层306之前移除金属氧化物层305。
根据本公开内容，通过下述方式方法200开始于210且如图3A和3B所描绘的：使金属表面接触一或多种金属卤化物、诸如金属氯化物或金属氟化物及类似物，以形成暴露的金属表面308。通过选择诸如金属氯化物或金属氟化物的一或多种金属卤化物，暴露的金属表面308形成为无金属氧化物层305或实质上无金属氧化物层305，并且暴露的金属表面308无法使自组装单层(SAM)与该表面结合。暴露的金属表面的材料的非限制性实例包括：实质上纯的、例如是实质上无氧化物的铜(Cu)、钴(Co)、钨(W)、铌(Nb)、钌(Ru)或钼(Mo)及诸如合金及类似物的上述材料的组合。
在实施方式中，诸如金属氯化物或金属氟化物的这一或多种金属卤化物以足以移除金属氧化物层305的量接触金属表面302。例如，诸如金属氯化物或金属氟化物的这一或多种金属卤化物可以在金属表面302顶上蚀刻金属氧化物层305，以形成暴露的金属表面308，如图3B所示。在多个实施方式中，使用足以移除金属氧化物层305的一或多种金属卤化物的量在适合反应的条件下使金属表面302接触一或多种金属卤化物，所述一或多种金属卤化物，诸如金属氯化物或金属氟化物。在实施方式中，使金属表面302接触诸如金属氯化物或金属氟化物的一或多种金属卤化物是在如下的第一温度执行：约300摄氏度至约400摄氏度、或约325摄氏度至约375摄氏度、或约325摄氏度、约350摄氏度、或约375摄氏度。在多个实施方式中，使金属表面302接触诸如金属氯化物或金属氟化物的一或多种金属卤化物是在下述量的压力下执行：1至15托、约1至约15托、约5托、约10托、或约15托。在实施方式中，使金属表面302接触诸如金属氯化物或金属氟化物的一或多种金属卤化物被执行达下述时间：约5至约20分钟，诸如约10分钟至约15分钟。在实施方式中，使金属表面与诸如金属氯化物或金属氟化物的一或多种金属卤化物接触被执行达5至20分钟。
在一些实施方式中，一或多种碱金属卤化物以足以移除金属氧化物层305的量接触金属表面302。例如，这一或多种碱金属卤化物可蚀刻金属表面302顶上的金属氧化物层305，以形成暴露的金属表面308，如图3B所示。在实施方式中，使用足以移除金属氧化物层305的一或多种碱金属卤化物的量在适合反应的条件下执行金属表面302与一或多种碱金属卤化物接触的步骤。在实施方式中，使金属表面302接触一或多种碱金属卤化物是在如下的第一温度执行：约300摄氏度至约400摄氏度、或约325摄氏度至约375摄氏度、或约325摄氏度、约350摄氏度、或约375摄氏度。在多个实施方式中，使金属表面302接触一或多种碱金属卤化物是在下述量的压力下执行：1至15托、约1至约15托、约5托、约10托、或约15托。在多个实施方式中，使金属表面302接触一或多种碱金属卤化物执行达下述时间：约5至约20分钟、诸如约10分钟至约15分钟。在实施方式中，使金属表面接触一或多种碱金属卤化物达5至20分钟。碱金属卤化物的非限制性实例包括：碱金属氟化物、碱金属氯化物、碱金属溴化物、碱金属碘化物、卤化锂、卤化钠、卤化钾、卤化铷、卤化铯、以及上述材料的组合。碱金属氟化物的实例包括氟化锂、氟化钠、氟化钾、氟化铷、氟化铯及上述材料的组合。碱金属氯化物的实例包括：氯化锂、氯化钠、氯化钾、氯化铷、氯化铯及上述材料的组合。碱金属氯化物的实例包括：氯化锂、氯化钠、氯化钾、氯化铷、氯化铯及上述材料的组合。
在实施方式中，一或多种金属卤化物是以足以移除金属氧化物层305的量接触金属表面302。例如，一或多种金属卤化物可蚀刻金属表面302顶上的金属氧化物层305，以形成暴露的金属表面308，如图3B所示。在多个实施方式中，使用足以移除金属氧化物层305的一或多种金属卤化物的量在适合反应的条件下执行金属表面302与一或多种金属卤化物接触的步骤。在实施方式中，使金属表面302接触一或多种金属卤化物是在如下的第一温度执行：约300摄氏度至约400摄氏度、或约325摄氏度至约375摄氏度、或约325摄氏度、约350摄氏度、或约375摄氏度。在实施方式中，使金属表面302接触一或多种金属卤化物是在下述量的压力下执行：1至15托、约1至约15托、约5托、约10托、或约15托。在实施方式中，使金属表面302接触一或多种金属卤化物执行达下述时间：约5至约20分钟，诸如约10分钟至约15分钟。在实施方式中，使金属表面接触一种或多种金属卤化物执行达5至20分钟。金属卤化物的实例包括：金属氟化物、金属氯化物、金属溴化物、金属碘化物及上述材料的组合。根据本发明使用的适合的一或多种金属氯化物的非限制性实例包括WClx、NbClx、RuClx、MoClx及上述材料的组合，其中x是整数或数字。
在实施方式中，使金属表面302接触诸如金属氯化物或金属氟化物的一或多种金属卤化物是在真空下执行，而使得氧无法抑制该反应或无法促进金属表面302顶上额外的金属氧化物材料生长。在实施方式中，使金属表面302接触诸如金属氯化物或金属氟化物的一或多种金属卤化物是在诸如图1的处理腔室的腔室中进行。图1的处理腔室可以是无氧的。
适合根据本公开内容使用的金属氯化物包括适合充分移除金属表面302顶上的金属氧化物层305而形成暴露的金属表面308的任何金属氯化物。根据本公开内容使用的适合的一或多种碱金属氯化物的非限制性实例包括WClx、NbClx、RuClx、MoClx或前述材料的组合，其中x是整数或数字。在实施方式中，氯化钨(WClx)是以气态形式提供，其中x是整数，例如大于1。在实施方式中，WClx是适合的反应物(其中x是整数，例如2、4、5、6、……)。在一个实施方式中，WClx是WCl6(六氯化钨)，其中x是整数6。在一些实施方式中，前驱物气体包括WCl5或WCl6。在实施方式中，RuClx适用于本文，其中X是2或3的整数，该RuClx例如为氯化钌(III)或氯化钌(RuCl2)。在实施方式中，诸如NbClx(x＝5、4)的氯化铌适用于本文。在实施方式中，适用于本文的金属氯化物可以以适于输送到在腔室中的基板的气态形式提供，例如以前驱物气体形式提供，所述腔室，例如是图1的处理腔室。在实施方式中，图1的处理腔室是无氧腔室。
金属氯化物与金属表面302反应的反应式的一个实例如下所示：
MOx+WClx↑加热→WCly↑+MClz↑+O2↑
在上述反应中，气相WCl蚀刻掉原生氧化物且在表面上留下纯金属，以形成暴露的金属表面。
金属氯化物与金属表面302反应的反应式的另一个实例如下所示：
MOx+WClx↑+H2↑加热→W↓+MClx↑+H2O↑
上述反应中，将氢气与WClx一起加入。结果，移除了天然氧化物。其他反应可适用于根据本公开内容的用途，包括在暴露的金属表面区域上沉积诸如钨(W)的金属的额外层的反应。
方法200在220继续，并且如图3C所描绘，在介电质表面304顶上生长或沉积自组装单层306，例如基于有机硅烷的自组装单层。在实施方式中，可挑选自组装单层306以在大于约50摄氏度(例如约100摄氏度至约500摄氏度)的第一温度下呈热稳定。通过选择在第一温度下热稳定的自组装单层306，可在低于300摄氏度(诸如约100摄氏度至约200摄氏度)的温度经由化学气相沉积(CVD)或原子层沉积(ALD)工艺执行自组装单层306的沉积，并且不会分解该自组装单层306。
在实施方式中，在介电质表面304顶上生长或沉积诸如基于有机硅烷的自组装单层之类的自组装单层306包括：使介电质表面304接触有机硅烷。在实施方式中，有机硅烷是气态形式，并且在真空下于腔室中输送。适合的有机硅烷具有长的烷基链，以形成紧密、无缺陷、热稳定、且化学惰性的阻挡物，该阻挡物能在稍后阶段干净地移除。适合的有机硅烷可包含C-8至C-30烷基链，包括具有C-8至多达C-30烷基链的所有相应的同系物(homologue)。示例性的适合的有机硅烷包括但不限于十八烷基三氯硅烷(ODTS)、三甲氧基(十八烷基)硅烷(ODTMS)、氯(二甲基)十八烷基硅烷(CDODS)、或三氯(1H,1H,2H,2H-全氟辛基)硅烷(PFTS)。选择有机硅烷分子的上述标准的其中一项可以是自组装单层的热稳定性。在实施方式中，选择在后续沉积的层310的沉积温度下热稳定的自组装单层避免了在随后沉积的层的沉积温度下自组装单层306的分解。例如，ODTS在二氧化硅(SiO2)上的热稳定性至少多达500摄氏度。因此，在经由ALD工艺沉积层310期间ODTS自组装单层不会分解。因此，SAM的热稳定性扩展了温度兼容性的极限。在实施方式中，生长基于有机硅烷的自组装单层是下述量的压力下执行：10至250托、100至350托、或250至350托。
在一些实施方式中，适合的有机胺基硅烷的非限制性实例可包括甲硅烷胺(silylamine)材料，包括美国专利申请第15/446,816号、由Kaufman-Osborn等人所发明、名称为“具有间歇性空气-水暴露的自组装单层阻挡”的专利申请案中描述的那些材料。
在一些实施方式中，适合用作本文SAM前驱物的甲硅烷基胺材料的非限制性实例包括：三(二甲胺基)甲基硅烷、三(二甲胺基)乙基硅烷、三(二甲胺基)丙基硅烷、三(二甲胺基)丁基硅烷、三(二甲胺基)戊基硅烷、三(二甲胺基)己基硅烷、三(二甲胺基)庚基硅烷、三(二甲胺基)辛基硅烷、三(二甲胺基)壬基硅烷、三(二甲胺基)癸基硅烷、三(二甲胺基)十一烷基硅烷、三(二甲胺基)十二烷基硅烷、三(二甲胺基)十三烷基硅烷、三(二甲胺基)十四烷基硅烷、三(二甲胺基)十五烷基硅烷、三(二甲胺基)十六烷基硅烷、三(二甲胺基)十七烷基硅烷、三(二甲胺基)十八烷基硅烷、三(二甲胺基)十九烷基硅烷、及上述材料的组合。
在一些实施方式中，用于本文的SAM分子的非限制性实例包括：二甲胺基三甲基硅烷，以及具有以下化学式的化学品：
Figure BDA0002942554590000081
或
Figure BDA0002942554590000082
及上述材料的组合。
在一些实施方式中，基于有机硅烷的自组装单层以气体前驱物形式提供，并且可包括例如一有机硅烷浓度，该浓度足以在介电质表面304上形成单层，足以阻止层310沉积在介电质表面上。在实施方式中，具有暴露的金属表面308和介电质表面304的基板300接触包含有机硅烷的气态前驱物材料达约2至约3小时，以在介电质表面304顶上形成自组装单层306。有机硅烷分子具有对介电质表面304的化学亲合力(例如，有反应性及选择性)。因此，自组装单层306将仅会在介电质表面304上形成而不会在暴露的金属表面308上形成。在实施方式中，在沉积自组装单层306之后，基板300停留或维持在真空下，以移除任何未吸收的有机硅烷分子。
接着，在230，且如图3D中所描绘，示出在基板300的暴露的金属表面308顶上选择性地沉积层310，其中自组装单层306抑制层310在介电质表面304顶上的沉积，该自组装单层306，诸如基于有机硅烷的自组装单层。图3D示出了层310选择性地沉积在基板300的暴露的金属表面308顶上。在一些实施方式中，经由任何适合的原子层沉积工艺或化学层沉积工艺进行层的沉积。介电质表面304顶上自组装单层306的存在抑制了在介电质表面304上层310的形成。在实施方式中，自组装单层306的热稳定性防止自组装单层306在层310的沉积温度(例如，低于约300摄氏度)下的分解。层310可包括适合用于半导体器件制造的任何材料。例如，在一些实施方式中，材料可以是第二低k材料或者是含硅材料，例如，诸如氧化硅(SiO2)。
接着，且如图3E所描绘，处理基板300，以从介电质表面304顶上移除自组装单层306。例如，基板300可以与远程等离子体接触，以从介电质表面304顶上移除自组装单层306。在一些实施方式中，其他移除工艺可包括使基板与水蒸气等离子体接触，以从介电质表面304顶上移除自组装单层306。在一些实施方式中，可将基板300加热到大于约500摄氏度的温度，例如是约500摄氏度至约1000摄氏度的温度，以从介电质表面304顶上移除自组装单层306。实施方式可包括，将基板加热至高于500摄氏度的温度。在移除自组装单层306之后，方法200结束，且可根据需求使基板历经进一步的处理，以完成半导体器件，诸如场效晶体管(FET)、鳍式场效晶体管(FinFET)、闪存器件、3D FINFET器件、或类似器件。
图4描绘了根据本公开内容的一些实施方式的调节具有金属表面和介电质表面的基板的方法的流程图。在实施方式中，提供一种调节具有金属表面和介电质表面的基板的方法。在实施方式中，该方法可包括使金属表面接触一或多种金属卤化物、诸如金属氯化物或金属氟化物，以形成暴露的金属表面，其中该暴露的金属表面抑制基于有机硅烷的自组装单层在该暴露的金属表面上的沉积。在一些实施方式中，使金属表面接触一或多种一或多种金属卤化物是在约300摄氏度至约400摄氏度的第一温度下、于1至15托的压力下进行达5至20分钟的持续时间，所述金属卤化物，诸如金属氯化物或金属氟化物。在多个实施方式中，金属氯化物是包含WClx、NbClx、RuClx、MoClx或上述材料的组合的气体，其中x是整数或数字。在其他实施方式中，使金属表面接触一或多种金属氯化物、金属氟化物、或上述材料的组合是在上述任何条件下执行。在多个实施方式中，这一或多种金属卤化物是包含WClx、NbClx、RuClx、MoClx或上述材料的组合的金属氯化物气体，其中x是整数或数字。
图1描绘了可用于实行如本文所讨论的本公开内容的实施方式的那种类型的说明性设备的示意图。设备100可包括控制器150和处理腔室102，该处理腔室102具有排气系统120，用于从处理腔室102的内部空间105移除多余的处理气体、处理副产物、或类似物。示例性处理腔室可包括被构造用于原子层沉积(ALD)或化学气相沉积(CVD)的许多种处理腔室中的任一种，这些处理腔室可购自美国加州Santa Clara的应用材料公司。可类似地使用来自其他制造商的其他适合的处理腔室。
处理腔室102具有内部空间105，该内部空间105可包括处理空间104。该处理空间104可以界定于例如基板支撑件108与一或多个气体入口之间，该基板支撑件108设置在处理腔室102内以用于在处理期间将基板110支撑在该基板支撑件108上，所述气体入口诸如设置在预定位置处的喷头114和/或喷嘴。在一些实施方式中，基板支撑件108可包括将基板110保持或支撑在基板支撑件108的表面上的机构，诸如静电吸盘、真空吸盘、基板保持夹具、或类似机构(未示出)。在一些实施方式中，基板支撑件108可包括用于控制基板温度的机构(诸如加热和/或冷却的装置，未示出)和/或用于控制基板表面附近的物种的通量和/或离子能量的机构。
例如，在一些实施方式中，基板支撑件108可包括RF偏压电极140。该RF偏压电极140可通过一个或多个各自的匹配网络(示出匹配网络136)耦接一个或多个偏压电源(示出一个偏压电源138)。这一或多个偏压电源能够以约2MHz至约60MHz的频率产生多达1200W或RF能量，该频率诸如为约2MHz、或约13.56MHz、或约60Mhz。在一些实施方式中，可以设置两个偏压电源，以用于通过各自的匹配网络将RF功率以约2MHz和约13.56MHz的相应的频率耦合到RF偏压电极140。至少一个偏压电源可以提供连续或脉冲功率。在一些实施方式中，偏压电源可替代地可以是DC或脉冲DC源。
基板110可经由处理腔室102的壁中的开口112进入处理腔室102。可经由狭缝阀118或者其他选择性提供穿过开口112进出腔室内部的机构选择性地密封开口112。基板支撑件108可耦接升降机构134，该升降机构134可控制基板支撑件108在下方位置(如图所示)与可选的上方位置之间的位置，该下方位置适合经由开口112将基板传送到腔室中和从腔室中传送出，该上方位置适合用于处理。可以选择处理位置以最大化特定工艺的处理均匀性。当处于升高的处理位置中的至少一个时，基板支撑件108可设置在开口112上方，以提供对称的处理区域。
一或多个气体入口(例如，喷头114)可以耦接气体供应源116，以用于通过质量流量控制器117将一或多种处理气体提供到处理腔室102的处理空间104中。此外，可以设置一或多个阀119以控制一或多种处理气体的流量。该质量流量控制器117和一或多个阀119可单独使用，或相结合使用以提供恒定流速、预定流速的处理气体或是脉冲的处理气体(如上文所述)。
尽管图1中显示喷头114，但可设置额外的或替代性的气体入口，诸如配置在处理腔室102的顶板中或在处理腔室102的侧壁上、或处于适合提供气体至处理腔室102的其他位置处的喷嘴或入口，该其他位置诸如处理腔室的底座、基板支撑件的周边、或类似位置。
设备100可利用电容耦合的RF能量以进行等离子体处理。举例而言，处理腔室102可具有由介电材料制成的顶板142和至少部分导电的喷头114，以提供RF电极(或者可以提供分别的RF电极)。喷头114(或其他RF电极)可通过一或多个各自的匹配网络(示出匹配网络146)耦接一或多个RF电源(示出一个RF电源148)。一或多个等离子体源能够在约2MHz和/或约13.56MHz的频率或诸如27MHz及/或60MHz的高频率产生多达约3,000W的RF能量，或者在一些实施方式中，多达约5,000W的RF能量。排气系统120通常包括泵送气室124和一或多个导管，所述导管将泵送气室124耦接处理腔室102的内部空间105(并且通常是处理空间104)。
真空泵128可经由泵送通口126耦接泵送气室124，用于经由一或多个排气通口(示出两个排气通口122)从处理腔室抽空废气。真空泵128可流体耦接排气出口132，用于将废气引导到适当的排气处理设备。阀130(例如闸阀，或类似物)可设置在泵送气室124中，以结合真空泵128的操作而助于控制废气的流速。尽管图中示出z-活动闸阀，但可利用任何适合的、工艺兼容的阀以控制废气流量。
为了助于如上所述的处理腔室102的控制，控制器150可以是任何形式的通用计算机处理器，该处理器能够在工业设施中使用，以控制各种腔室和子处理器。CPU 152的内存或CPU 152的计算机可读媒体156可以是易于取得的存储器中的一或多种，诸如随机存取存储器(RAM)、只读存储器(ROM)、软盘、硬盘或任何其他形式的本地端或远程数字储存装置。支持电路154耦接CPU152，以用常规方式支持处理器。这些电路包括高速缓冲储存器、电源供应器、频率电路、输入/输出电路及子系统、与类似物。
本文公开的方法一般地可储存在内存156中作为软件例程158，当由CPU152执行时，该软件例程158引发处理腔室102执行本公开内容的工艺。软件例程158也可以由第二CPU(图中未示)储存和/或执行，该第二CPU位在CPU 152所控制的硬件的远程。本公开内容的一些或全部方法也可以在硬件中执行。就此而言，本公开内容可在软件中实现且在硬件中使用计算机系统执行，例如作为专用集成电路或其他类型的硬件实现方式的应用，或者作为软件和硬件的组合。可以在将基板110定位在基板支撑件108上之后执行软件例程158。当由CPU152执行该软件例程158时，该软件例程158将该通用计算机转换成专用计算机(控制器150)，该专用计算机控制腔室操作，使得本文公开的方法得以执行。
在一些实施方式中，本公开内容涉及一种处理腔室，该处理腔室被构造用于执行在具有金属表面和介电质表面的基板顶上选择性沉积层的方法，该方法包括：(a)使该金属表面接触一种或多种金属卤化物，以形成暴露的金属表面；(b)在该介电质表面顶上生长基于有机硅烷的自组装单层；及(c)在该基板的该暴露的金属表面顶上选择性地沉积一层，其中该基于有机硅烷的自组装单层抑制该层在该介电质表面顶上的沉积。
在一些实施方式中，本公开内容涉及一种计算机可读媒体，在该计算机可读媒体上储存有数个指令，当执行这些指令时，这些指令引发处理腔室执行在具有金属表面和介电质表面的基板顶上选择性沉积层的方法，该方法包括：(a)使该金属表面接触一种或多种金属卤化物，而形成暴露的金属表面；(b)在该介电质表面顶上生长基于有机硅烷的自组装单层；及(c)在该基板的该暴露的金属表面顶上选择性地沉积一层，其中该基于有机硅烷的自组装单层抑制该层在该介电质表面顶上的沉积。
在一些实施方式中，本公开内容关于一种计算机可读媒体，在该计算机可读媒体上储存有数个指令，当执行这些指令时，这些指令引发一种调节具有金属表面和介电质表面的基板的方法，该方法包括：使该金属表面接触一或多种金属卤化物，以形成暴露的金属表面，其中该暴露的金属表面抑制基于有机硅烷的自组装单层在该暴露的金属表面上的沉积。
在一些实施方式中，本公开内容涉及一种计算机可读媒体，在该计算机可读媒体上储存有数个指令，当执行这些指令时，这些指令引发一种在具有金属表面和介电质表面的基板顶上选择性沉积层的方法，该方法包括：(a)使该金属表面接触金属氯化物、金属氟化物、或上述材料的组合中的一或多种，以形成暴露的金属表面；(b)在该介电质表面顶上生长基于有机硅烷的自组装单层；及(c)在该基板的该暴露的金属表面顶上选择性地沉积一层，其中该基于有机硅烷的自组装单层抑制该层在该介电质表面顶上的沉积。
可以使用其他半导体基板处理系统实行本公开内容，其中本发明所属技术领域的技术人员可通过利用本文公开的教示在不脱离本公开内容的精神的情况下调整处理参数以达成可接受的特性。
虽然前述内容针对本公开内容的实施方式，但是在不脱离本公开内容的基本范畴的情况下可设计本公开内容的其他和进一步的实施方式。

Claims (15)

1.一种在具有金属表面和介电质表面的基板顶上选择性沉积一层的方法，包括以下步骤：
(a)使所述金属表面接触一或多种金属卤化物，以形成暴露的金属表面；
(b)在所述介电质表面顶上生长基于有机硅烷的自组装单层；及
(c)在所述基板的所述暴露的金属表面顶上选择性地沉积一层，其中所述基于有机硅烷的自组装单层抑制所述层在所述介电质表面顶上的沉积。
2.如权利要求1所述的方法，其中使所述金属表面接触一或多种金属卤化物的步骤是在第一温度执行，所述第一温度为约300摄氏度至约400摄氏度。
3.如权利要求1或2所述的方法，其中使所述金属表面接触一或多种金属卤化物是在一压力执行，所述压力的量为1托至15托。
4.如权利要求1至3任一项所述的方法，其中使所述金属表面接触一或多种金属卤化物的步骤被执行达5至20分钟。
5.如权利要求1至4任一项所述的方法，其中所述一或多种金属卤化物是气体。
6.如权利要求1至5任一项所述的方法，其中所述一或多种金属卤化物是金属氯化物，所述金属氯化物包括WClx、NbClx、RuClx、MoClx、或上述材料的组合，其中x是整数。
7.如权利要求1至6任一项所述的方法，其中所述使所述金属表面接触一或多种金属卤化物的步骤是在无氧腔室中执行。
8.如权利要求1至7任一项所述的方法，其中使所述金属表面接触一或多种金属卤化物的步骤在所述金属表面顶上形成暴露的金属表面。
9.如权利要求1至8任一项所述的方法，其中生长所述基于有机硅烷的自组装单层的步骤包括：将所述基板暴露至气体，所述气体包括有机硅烷。
10.如权利要求1至9任一项所述的方法，其中所述基于有机硅烷的自组装单层包括C-8至C-30的烷基链。
11.如权利要求1至10任一项所述的方法，其中生长所述基于有机硅烷的自组装单层的步骤是在第一温度执行，所述第一温度为约100摄氏度至约200摄氏度。
12.如权利要求1至10任一项所述的方法，其中生长所述基于有机硅烷的自组装单层的步骤是在一压力执行，所述压力的量为10托至350托。
13.如权利要求1至12任一项所述的方法，其中生长所述基于有机硅烷的自组装单层的步骤被执行达约2小时至3小时的持续时间。
14.如权利要求1至13任一项所述的方法，其中生长所述基于有机硅烷的自组装单层的步骤是在无氧腔室中执行，且所述基于有机硅烷的自组装单层包括三(二甲胺基)十八烷基硅烷。
15.一种计算机可读媒体，在所述计算机可读媒体上储存有数个指令，当执行所述指令时，所述指令引发处理腔室执行在具有金属表面和介电质表面的基板顶上选择性沉积一层的方法，所述方法包括以下步骤：(a)使所述金属表面接触一种或多种金属卤化物，以形成暴露的金属表面；(b)在所述介电质表面顶上生长基于有机硅烷的自组装单层；及(c)在所述基板的所述暴露的金属表面顶上选择性地沉积一层，其中所述基于有机硅烷的自组装单层抑制所述层在所述介电质表面顶上的沉积。
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