CN107258010A - 使用烷基胺的选择性移除金属氮化物的方法及设备 - Google Patents
使用烷基胺的选择性移除金属氮化物的方法及设备 Download PDFInfo
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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Abstract
本文提供用于相对于暴露的或下方的介电或金属层选择性移除金属氮化物的改良方法和设备。在一些实施方式中,一种蚀刻在基板顶上的金属氮化物层的方法包括以下步骤:(a)氧化金属氮化物层以在该金属氮化物层的表面形成金属氮氧化物层(MN1‑xOx),其中M为钛或钽中的一种并且x为从0.05至0.95的整数;以及(b)使该金属氮氧化物层(MN1‑xOx)暴露于处理气体,其中该金属氮氧化物层(MN1‑xOx)与该处理气体反应以形成挥发性化合物,该挥发性化合物从该金属氮化物层的该表面解吸。
Description
技术领域
本公开内容的实施方式总体涉及将烷基胺使用于金属氮化物的选择性移除的方法及设备。
背景技术
诸如氮化钛(TiN)和氮化钽(TaN)之类的金属氮化物材料常用在半导体产业中的许多半导体应用,例如作为掩蔽材料或作为阻挡材料。然而,选择性移除金属氮化物掩蔽材料而不损伤其他结构(例如暴露的或下方的介电或金属层)是非常困难的。当基于溶液或基于等离子体的方法并非可行的和/或理想的时,选择性移除金属氮化物掩蔽材料而不损伤其他结构的问题变得更加困难。
因此,本发明人开发了用于选择性地相对于暴露的或下方的介电或金属层移除金属氮化物的改良方法和设备。
发明内容
本文提供用于相对于暴露的或下方的介电或金属层选择性移除金属氮化物的方法和设备。在一些实施方式中,一种蚀刻在基板顶上的金属氮化物层的方法包括以下步骤:(a)氧化金属氮化物层以在该金属氮化物层的表面形成金属氮氧化物层(MN1-xOx),其中M为钛或钽中的一种并且x为从0.05至0.95的整数;以及(b)使该金属氮氧化物层(MN1-xOx)暴露于处理气体,其中该金属氮氧化物层(MN1-xOx)与该处理气体反应以形成挥发性化合物,该挥发性化合物从该金属氮化物层的该表面解吸。
在一些实施方式中,一种蚀刻在基板顶上的氮化钛层的方法,包括以下步骤:使氮化钛层暴露于处理气体,该处理气体通过蒸发处理溶液形成,该处理溶液包含二乙胺和水,其中该氮化钛层与该处理气体反应以形成挥发性化合物,该挥发性化合物从该氮化钛层的表面解吸。
在一些实施方式中,一种用于蚀刻在基板顶上的金属氮化物层的设备,包括:反应器主体,该反应器主体包含用以容纳液体处理溶液的处理容积、在第一端的主体凸缘、及第一加热器,该第一加热器在与该第一端相对的第二端嵌入该反应器主体内或耦接到该反应器主体,用以加热该液体处理溶液;反应器盖体,该反应器盖体包含在第一端且与该主体凸缘相配合而构造的盖体凸缘;环形夹,该环形夹经构造以在该盖体凸缘和该主体凸缘将该反应器主体夹紧到该反应器盖体;真空夹盘,该真空夹盘嵌入该反应器盖体内并经构造以将基板固持在该处理容积内,使得设置在该基板上的金属氮化物层面向该处理容积的底部;第二加热器,该第二加热器嵌入该反应器盖体内或耦接到该反应器盖体并经构造以加热该基板;以及排气系统,该排气系统耦接到该反应器主体以去除来自该处理容积的处理副产物。
以下讨论本公开内容的其他的实施方式及其变型。
附图说明
可以参照附图中绘示的本公开内容的说明性实施方式来理解以上简要概述的和以下更详细讨论的本公开内容的实施方式。附图仅图示本公开内容的典型实施方式,因而不应视为对本发明的范围的限制,因为本公开内容可允许其他等同有效的实施方式。
图1描绘依据本公开内容的一些实施方式蚀刻在基板顶上的金属氮化物层的方法的流程图。
图2A-2C描绘依据本公开内容的一些实施方式蚀刻在基板顶上的金属氮化物层的阶段。
图3描绘依据本公开内容的一些实施方式的适合进行蚀刻在基板顶上的金属氮化物层的方法的设备的横截面图。
为了便于理解,已尽可能地使用相同的附图标号来标示附图中共通的相同的元件。附图式未依比例绘制,而且可以为了清楚而简化。可以将一个实施方式的元件和特征在没有进一步地描述下有益地并入其他实施方式中。
具体实施方式
本文提供用于相对于暴露的或下方的介电或金属层选择性移除金属氮化物的方法和设备。在一些实施方式中,本文描述的发明方法有利地提供相对于暴露的或下方的介电或金属层选择地蚀刻用作掩蔽材料的金属氮化物的创新方法,该介电或金属层例如可自美国加州圣克拉拉的应用材料公司购得的BLACK电介质材料(下文称为“黑金刚石”或“BD”)或二氧化硅层(例如SiOx)。本文描述的发明方法也可用于其他可能需要蚀刻金属氮化物的半导体制造应用。在一些实施方式中,胺基溶液被汽化并施加到金属氮化物材料来从结构的顶部选择性蚀刻金属氮化物材料而不损伤例如下方的或暴露的黑金刚石、二氧化硅、和/或铜(Cu)结构。
图1为依据本公开内容的一些实施方式蚀刻在基板顶上的金属氮化物层的方法100的流程图。图2A-2C为依据本公开内容的一些实施方式在图1的处理程序的不同阶段期间的基板的横截面图。本发明的方法可以在适当的反应器容器中进行,例如以下针对图3讨论的反应器容器。
图3描绘适用于执行方法200的反应器容器300的横截面图。反应器容器300是一个闭环(closed loop)控制系统,该闭环控制系统在反应器容器300中的湿润部件使用的材料与下述的方法200中使用的化学物质相容。图3描绘的反应器容器300包含反应器主体302和反应器盖体304。反应器主体302和反应器盖体304包含适当的开口,用于添置如下所述的传感器、电源、及真空输入。反应器主体302包含处理容积306。处理容积306容纳下述的方法100中使用的适当液体处理溶液318。在一些实施方式中,处理容积306可以容纳多达约200ml至约300ml的适当液体处理溶液318。
反应器主体302和反应器盖体是由适合承受在下述方法200中使用的温度和压力的材料制成。在一些实施方式中,反应器主体302和反应器盖体是由涂有例如Teflon或Magnaplate 10K的不锈钢(SST)材料制成。涂层可以基于与方法200中使用的化学物质、温度及压力的相容性来选择。反应器主体302包含在第一端324的主体凸缘322。反应器盖体304包含在第一端328且与主体凸缘322相配合而构造的盖体凸缘326。用盖体凸缘326且带有防漏O形环330密封件夹紧主体凸缘322。主体凸缘322具有斜切的背表面356。盖体凸缘326具有斜切的背表面358。主体凸缘322和盖体凸缘326通过环形夹332相配合,环形夹332由斜切的背表面356、358附近的螺钉334紧固。
在O形环330的附近添置冷却通道336,以保护O形环330免于高温。出于安全的目的,还将冷却通道336设置在反应器盖体304的顶部上,以将外反应器盖体304的温度保持在低于约70℃。将适当的入口344和出口346耦接到冷却通道336以供应和去除冷却流体,例如来自冷却通道336的水。反应器主体302的外壁338用绝缘护套340覆盖,以避免处理气体冷凝并防止高温表面。
耦接到真空源360的真空夹盘308嵌入反应器盖体304内并经构造以将基板314固持在处理容积306内。真空夹盘308固持基板314,使得设置在基板314上的金属氮化物层面向处理容积306的底部316。
例如,使用在第二端362处嵌入反应器主体302内或耦接到反应器主体302的第一加热器310,来加热处理容积306内的液体处理溶液318。第一加热器310耦接到适当的电源(未图示)。第一加热器310将液体处理溶液318加热到足以蒸发溶剂的温度。
在一些实施方式中,例如,使用嵌入反应器盖体304内或耦接到反应器盖体304的第二加热器312,来加热基板314。第二加热器312耦接到适当的电源(未图示)。在一些实施方式中,第一加热器310和第二加热器312可以处在相同的温度。在一些实施方式中,第一加热器310和第二加热器312可以处在不同的温度。在一些实施方式中,第一加热器可以处在约25摄氏度至约300摄氏度的温度。在一些实施方式中,第二加热器处在比第一加热器更高的温度,以避免蒸汽冷凝到基板314上。在一些实施方式中,第二加热器312处在比第一加热器的温度高约10度至约15度的温度。
在一些实施方式中,将反应器盖体304夹紧到反应器主体302的顶部,以密封处理容积306。在一些实施方式中,例如,还使用反应器主体302内的加热线圈,来加热反应器主体302。加热反应器主体302防止蒸汽冷凝到处理容积306的内表面壁320上。
通过反应器主体302中的开口342将液体处理溶液318注射到处理容积306内。使用手动阀364以从处理容积306排出液体处理溶液318。
耦接到反应器主体302的闭环控制排气系统348接收来自压力转换器350设定的反馈以触发气动阀352经由过压管线354释放方法200的副产物,例如,到洗涤器。由热电偶354与具有加热器控制器的过热开关366来保持温度循环反馈。
如图2A描绘的,于步骤102由氧化在基板202顶上氧化金属氮化物层204开始方法100。基板202可以是任何适当的基板,例如半导体晶片。也可以使用具有其他几何形状的基板,例如矩形、多边形、或其他几何构形。在一些实施方式中,基板202可以包括第一层216。第一层216可以是基板202的基底材料(例如基板本身)、或在基板上形成的层。例如,在一些实施方式中,第一层216可以是适用于在第一层216内形成特征的层。例如,在一些实施方式中,第一层216可以是电介质层,例如氧化硅(SiO2)、氮化硅(SiN)、低介电常数材料、或类似物。在一些实施方式中,低介电常数材料可以是掺杂碳的电介质材料(例如掺杂碳的氧化硅(SiOC)、可从加州圣克拉拉的应用材料公司购得的BLACK电介质材料、或类似物)、有机聚合物(例如聚酰亚胺、聚对二甲苯、或类似物)、掺杂有机物的硅玻璃(OSG)、掺杂氟的硅玻璃(FSG)、或类似物。在一些实施方式中,第一层216可以是铜层。
在一些实施方式中,金属氮化物层204是氮化钛(TiN)或氮化钽(TaN)。在一些实施方式中,金属氮化物层204是使用半导体制造产业中公知的任何适当沉积工艺沉积的,例如物理气相沉积(PVD)工艺或化学气相沉积(CVD)工艺。在一些实施方式中,金属氮化物层可以是用于形成特征的掩蔽层,该特征例如下层中的通孔或沟槽。金属氮化物层204的氧化在金属氮化物层204的表面214形成金属氮氧化物层(MN1-xOx)208,其中M为钛或钽中的一种并且x为从0.05至0.95的整数。
在如图2A描绘的一些实施方式中,金属氮化物层204是通过使金属氮化物层204暴露于含氧气体206而被氧化。在一些实施方式中,含氧气体是氧(O2)气体或臭氧(O3)气体或上述气体的组合。在一些实施方式中,以约2sccm至约20sccm的流动速率提供含氧气体206持续约2秒至约30秒。
接着,在步骤104并如图2B所描绘,使金属氮氧化物层(MN1-xOx)208暴露于处理气体210。处理气体210与金属氮氧化物层(MN1-xOx)208的反应在金属氮化物层204的顶上形成挥发性化合物212,挥发性化合物212从金属氮化物层204的表面214解吸。挥发性化合物212在处理气体210形成的温度下从金属氮化物层204的表面214解吸,因此不需要单独的退火工艺来使挥发性化合物212解吸。在一些实施方式中,通过将反应器容器300内的液体处理溶液至少加热到该液体处理溶液的沸点来产生处理气体210。在一些实施方式中,该处理溶液包含具有化学式R1R2NH的二级胺的蚀刻剂前驱物,其中R1和R2可以是烷基,例如甲基、乙基、丙基或丁基。在一些实施方式中,蚀刻剂前驱物是二乙胺、叔丁胺、亚乙基二胺、三乙胺、二环己胺、羟基胺、二丙胺、二丁胺、丁胺、异丙胺、或丙胺。
在一些实施方式中,将液体处理溶液至少加热到液体处理溶液的沸点的温度,或在一些实施方式中至少加热到高于液体处理溶液的沸点的温度。所属技术领域中普通技术人员将理解的是,液体处理溶液被加热到的最高温度是受到选择的蚀刻剂前驱物分子的分解温度所限制。例如,在一些实施方式中,包含二乙胺(具有约55摄氏度的沸点)的处理溶液被加热到约80摄氏度至约175摄氏度的温度。例如,在一些实施方式中,包含二环己胺(具有约255摄氏度的沸点)的处理溶液被加热到高达约300摄氏度的温度。本发明人还观察到,增加蚀刻剂前驱物的量(例如从约5ml至约30ml)并利用较高的温度来蒸发处理溶液(尽管仍受选择的蚀刻剂前驱物分子的分解温度所限制)导致反应器容器300内的压力增大,此举改善金属氮化物层204的蚀刻速度。发明人已观察到,约1大气压(atm)至约10atm的压力范围,例如,约7atm,改善了金属氮化物层204的蚀刻速度。在一些实施方式中,使金属氮氧化物层(MN1-xOx)208暴露于处理气体210持续约10秒至1200秒,例如持续约10秒至约300秒,例如持续约60秒至约1200秒。
在一些实施方式中,在反应器容器300内进行金属氮化物层204的氧化而没有如上所述的暴露于含氧气体(即原位氧化)。在原位氧化的实施方式中,未使金属氮化物层暴露于初始含氧气体。取而代之的是,液体处理溶液包含蚀刻剂前驱物和水的混合物。在一些实施方式中,液体处理溶液是由蚀刻剂前驱物和水的混合物所组成、或本质上由蚀刻剂前驱物和水的混合物所组成。在一些实施方式中,液体处理溶液包含约0.1重量%至约5重量%的水,其余为蚀刻剂前驱物。与金属氮化物层204经由暴露于含氧气体而氧化的初始氧化相比,本发明人已观察到,在液体处理溶液中加入水,图2B示出的处理气体210可以有利地在单一步骤中氧化和蚀刻金属氮化物层204并且进一步地改善金属氮化物层204的蚀刻速度。例如,进行原位氧化产生约3至4埃/分钟的金属氮化物层204蚀刻速度,而单独的氧化步骤产生较低的金属氮化物层204蚀刻速度。
在一些实施方式中,可以重复方法100来将金属氮化物层204蚀刻到预定的厚度。例如,在一些实施方式中,重复方法100以完全或实质上完全蚀刻金属氮化物层204而没有损坏下方的第一层216。
虽然前述内容针对本公开内容的实施方式,但在不偏离本发明的基本范围的前提下仍可设计出本公开内容的其他的和进一步的实施方式。
Claims (15)
1.一种蚀刻在基板顶上的金属氮化物层的方法,包含以下步骤:
(a)氧化金属氮化物层以在所述金属氮化物层的表面形成金属氮氧化物层(MN1-xOx),其中M为钛或钽中的一种并且x为从0.05至0.95的整数;以及
(b)使所述金属氮氧化物层(MN1-xOx)暴露于处理气体,其中所述金属氮氧化物层(MN1- xOx)与所述处理气体反应以形成挥发性化合物,所述挥发性化合物从所述金属氮化物层的所述表面解吸。
2.如权利要求1所述的方法,进一步包含以下步骤:
重复(a)-(b)以将所述金属氮化物层蚀刻到预定厚度。
3.如权利要求1至2中任一项所述的方法,其中在使所述金属氮氧化物层(MN1-xOx)暴露于所述处理气体之前氧化所述金属氮化物层。
4.如权利要求3所述的方法,其中经由使所述金属氮化物层暴露于含氧气体来氧化所述金属氮化物层。
5.如权利要求4所述的方法,其中所述含氧气体包含氧(O2)气体或臭氧(O3)气体。
6.如权利要求1至2中任一项所述的方法,其中使所述金属氮氧化物层(MN1-xOx)暴露于处理气体的步骤进一步包含以下步骤:将液体处理溶液至少加热到所述液体处理溶液的沸点。
7.如权利要求6所述的方法,其中所述液体处理溶液包含蚀刻剂前驱物,并且其中所述蚀刻剂前驱物包含二乙胺、叔丁胺、亚乙基二胺、三乙胺、二环己胺、羟基胺、二丙胺、二丁胺、丁胺、异丙胺、或丙胺。
8.如权利要求1至2中任一项所述的方法,其中氧化所述金属氮化物层与使所述金属氮氧化物层(MN1-xOx)暴露于所述处理气体同时发生。
9.如权利要求8所述的方法,其中使所述金属氮氧化物层(MN1-xOx)暴露于所述处理气体的步骤进一步包含以下步骤:将液体处理溶液至少加热到所述液体处理溶液的沸点,所述液体处理溶液包含蚀刻剂前驱物与水的混合物。
10.如权利要求9所述的方法,其中所述蚀刻剂前驱物包含二乙胺、叔丁胺、亚乙基二胺、三乙胺、二环己胺、羟基胺、二丙胺、或二丁胺。
11.如权利要求1至2中任一项所述的方法,进一步包含以下步骤:在约1大气压至约10大气压的压力下使所述金属氮氧化物层(MN1-xOx)暴露于所述处理气体持续约60秒至约1200秒。
12.如权利要求1至2中任一项所述的方法,其中使所述金属氮氧化物层(MN1-xOx)暴露于所述处理气体的步骤进一步包含以下步骤:在反应器容器内使所述金属氮氧化物层(MN1- xOx)暴露于所述处理气体,所述反应器容器包含反应器主体和反应器盖体。
13.如权利要求12所述的方法,其中所述反应器主体包含处理容积,所述处理容积经构造以容纳液体处理溶液。
14.如权利要求13所述的方法,其中所述反应器盖体包含真空夹盘,所述真空夹盘耦接到所述反应器盖体并经构造以将所述基板固持在所述处理容积内,并且其中所述反应器主体包含第一加热器,所述第一加热器经构造以将所述液体处理溶液加热到足以蒸发所述液体处理溶液的温度,并且所述反应器盖体包含第二加热器,用以加热所述基板。
15.一种用于蚀刻在基板顶上的金属氮化物层的设备,包含:
反应器主体,所述反应器主体包含:用以容纳液体处理溶液的处理容积、在第一端的主体凸缘、及第一加热器,所述第一加热器在与所述第一端相对的第二端嵌入所述反应器主体内或耦接到所述反应器主体,用以加热所述液体处理溶液;
反应器盖体,所述反应器盖体包含在第一端处与所述主体凸缘相配合而构造的盖体凸缘;
环形夹,所述环形夹经构造以在所述盖体凸缘和所述主体凸缘将所述反应器主体夹紧到所述反应器盖体;
真空夹盘,所述真空夹盘嵌入所述反应器盖体内并经构造以将基板固持在所述处理容积内,使得设置在所述基板上的金属氮化物层面向所述处理容积的底部;
第二加热器,所述第二加热器嵌入所述反应器盖体内或耦接到所述反应器盖体并经构造以加热所述基板;以及
排气系统,所述排气系统耦接到所述反应器主体以释放来自所述处理容积的处理副产物。
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TW201703130A (zh) | 2017-01-16 |
JP2018511935A (ja) | 2018-04-26 |
WO2016138218A8 (en) | 2017-03-16 |
US20180033643A1 (en) | 2018-02-01 |
KR20170121243A (ko) | 2017-11-01 |
WO2016138218A1 (en) | 2016-09-01 |
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