CN111554577B - 基板处理方法和成膜系统 - Google Patents

基板处理方法和成膜系统 Download PDF

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CN111554577B
CN111554577B CN202010078882.9A CN202010078882A CN111554577B CN 111554577 B CN111554577 B CN 111554577B CN 202010078882 A CN202010078882 A CN 202010078882A CN 111554577 B CN111554577 B CN 111554577B
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gas
substrate
pretreatment
film
tungsten
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CN111554577A (zh
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成岛健索
平松永泰
堀田隼史
松本淳志
荒木真人
山崎英亮
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Tokyo Electron Ltd
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Abstract

本发明提供一种使低电阻的钨膜成膜的基板处理方法和成膜系统。一种基板处理方法,其具备如下工序:准备在表面形成有自然氧化膜的基板的工序;实施作为去除所述自然氧化膜的处理的前处理的工序;以及将载置所述基板的载物台的温度加热到预定的温度,向实施了所述前处理之后的所述基板供给氯化钨气体和还原气体而在所述基板直接使钨膜成膜的工序。

Description

基板处理方法和成膜系统
技术领域
本公开涉及一种基板处理方法和成膜系统。
背景技术
公知有在基板上使钨膜成膜的成膜方法。
在专利文献1中公开有通过使用TiN膜、TiSiN膜作为基底膜而使钨膜的成膜性良好的钨膜的成膜方法。
现有技术文献
专利文献
专利文献1:日本特开2015-193908号公报
发明内容
发明要解决的问题
在一方面,本公开提供一种使低电阻的钨膜成膜的基板处理方法和成膜系统。
用于解决问题的方案
为了解决上述问题,根据一技术方案,提供一种基板处理方法,该基板处理方法具备如下工序:准备在表面形成有自然氧化膜的基板的工序;实施作为去除所述自然氧化膜的处理的前处理的工序;以及将载置所述基板的载物台的温度加热到预定的温度,向实施了所述前处理之后的所述基板供给氯化钨气体和还原气体而在所述基板直接使钨膜成膜的工序。
发明的效果
根据一方面,能够提供使低电阻的钨膜成膜的基板处理方法和成膜系统。
附图说明
图1是本实施方式的群集系统的结构图。
图2是本实施方式的群集系统所具备的金属膜成膜装置的截面示意图的一个例子。
图3是表示本实施方式的群集系统的动作的一个例子的流程图。
图4是表示本实施方式的各工序中的基板的状态的截面示意图。
图5是表示ALD工艺的气体供给序列的一个例子的图。
图6是表示参考例的各工序中的基板的状态的截面示意图。
图7是表示参考例中的基底膜和钨膜的膜厚与电阻之间的关系的图表。
图8是对本实施方式的成膜速率与参考例的成膜速率进行对比的图表。
具体实施方式
以下,参照附图而对用于实施本公开的形态进行说明。在各附图中,存在如下情况:对同样构成部分标注相同附图标记,而省略重复的说明。
<群集系统>
使用图1而对本实施方式的群集系统(成膜系统)300进行说明。图1是本实施方式的群集系统300的结构图。群集系统300是用于对晶圆等基板W进行氧化膜去除处理、之后对实施了氧化膜去除处理的基板W进行金属膜成膜处理的装置。
群集系统300具有1个或多个处理装置。在图1所示的例子中,群集系统300具有:第1前处理装置100、第2前处理装置150以及金属膜成膜装置200。这些装置分别借助闸阀G与俯视形状呈七边形的真空输送室301的4个壁部连接。真空输送室301内利用真空泵排气而被保持在预定的真空度。
第1前处理装置100和第2前处理装置150是对基板W进行作为前处理的氧化膜去除处理的装置。在此,在基板W以预定的图案形成有沟槽403(参照随后论述的图4的(a))。另外,在沟槽403的底部的硅部分的表面形成有自然氧化膜404(参照随后论述的图4的(a))。在氧化膜去除处理中,去除在基板W的沟槽403的底部的硅部分的表面形成的自然氧化膜404。具体而言,第1前处理装置100进行用于去除自然氧化膜404的COR(化学氧化物去除:Chemical Oxide Removal)处理。第2前处理装置150进行用于去除因COR处理而产生的反应生成物405的PHT(后热处理:Post Heat Treatment)处理。
在此,COR处理是如下工序:向第1前处理装置100的腔室内供给处理气体,对在基板W形成的氧化硅(自然氧化膜404)进行蚀刻。例如,作为处理气体,供给作为含氟气体的氟化氢气(HF)、作为含氮气体的氨气(NH3)、氩气(Ar)、氮气(N2)。由此,基板W被暴露于含氟气体与含氮气体的混合气体。基板W的氧化硅通过与氟化氢气体、氨气发生反应,从而生成氟硅酸铵((NH4)SiF6):AFS作为反应生成物(副生成物)。此外,COR处理的反应生成物405(参照随后论述的图4的(b))堆积于基板W上。
PHT处理是指,通过对基板W进行加热,使基板W上的反应生成物405升华而去除。
金属膜成膜装置200是进行金属膜成膜处理的装置。在金属膜成膜处理中,在基板W的沟槽403的底部的硅部分使钨膜406(参照随后论述的图4的(d))成膜。金属膜成膜装置200包括例如CVD(化学气相沉积:Chemical Vapor Deposition)装置、ALD(原子层沉积:Atomic Layer Deposition)装置等。
另外,在真空输送室301的其他3个壁部借助闸阀G1连接有3个加载互锁室302。隔着加载互锁室302在真空输送室301的相反侧设置有大气输送室303。3个加载互锁室302借助闸阀G2与大气输送室303连接。加载互锁室302于在大气输送室303与真空输送室301之间输送基板W之际在大气压与真空之间对压力进行控制。
在大气输送室303的与加载互锁室302安装壁部相反的一侧的壁部具有用于安装载体(FOUP等)C的3个载体安装口305,该载体(FOUP等)C用于收纳基板W。另外,在大气输送室303的侧壁设置有进行基板W的对准的对准腔室304。在大气输送室303内形成有洁净空气的下降流。
在真空输送室301内设置有输送机构306。输送机构306向第1前处理装置100、第2前处理装置150、金属膜成膜装置200、加载互锁室302输送基板W。输送机构306也可以具有能够独立地移动的两个输送臂307a、307b。
在大气输送室303内设置有输送机构308。输送机构308向载体C、加载互锁室302、对准腔室304输送基板W。
群集系统300具有整体控制部310。整体控制部310具有:主控制部、输入装置(键盘、鼠标等)、输出装置(打印机等)、显示装置(显示器等)、存储装置(存储介质),该主控制部具有对第1前处理装置100、第2前处理装置150以及金属膜成膜装置200的各构成部、真空输送室301的排气机构、输送机构306、加载互锁室302的排气机构、气体供给机构、大气输送室303的输送机构308、闸阀G、G1、G2的驱动系统等进行控制的CPU(计算机)。整体控制部310的主控制部例如基于在内置到存储装置的存储介质、或装载到存储装置的存储介质存储的处理制程来使群集系统300执行预定的动作。此外,整体控制部310也可以是随后论述的控制装置6(参照图2)那样的各单元的控制部的上位的控制部。
接着,对如以上这样构成的群集系统300的动作进行说明。以下的处理动作基于在整体控制部310中的存储介质存储的处理制程而被执行。
首先,整体控制部310利用输送机构308从与大气输送室303连接起来的载体C取出基板W而向大气输送室303输送。整体控制部310使任一个加载互锁室302的闸阀G2打开,将由输送机构308保持着的基板W向该加载互锁室302送入。在输送机构308的输送臂退避到大气输送室303之后,整体控制部310使闸阀G2关闭,对加载互锁室302内进行真空排气。此外,在将基板W从载体C取出来之后且向加载互锁室302送入之前,在对准腔室304进行基板W的对准。
在加载互锁室302成为预定的真空度的时间点,整体控制部310使加载互锁室302的闸阀G1打开,利用输送机构306从加载互锁室302取出基板W而向真空输送室301输送。在输送机构306的输送臂退避到真空输送室301之后,整体控制部310使闸阀G1关闭。
整体控制部310使第1前处理装置100的闸阀G打开,将由输送机构306保持着的基板W向该第1前处理装置100送入。在输送机构306的输送臂退避到真空输送室301之后,整体控制部310使闸阀G关闭,利用该第1前处理装置100进行COR处理。
COR处理结束后,整体控制部310使第1前处理装置100的闸阀G打开,利用输送机构306从第1前处理装置100取出基板W而向真空输送室301输送。在输送机构306的输送臂退避到真空输送室301之后,整体控制部310使第1前处理装置100的闸阀G关闭。
整体控制部310使第2前处理装置150的闸阀G打开,将由输送机构306保持着的基板W向该第2前处理装置150送入。在输送机构306的输送臂退避到真空输送室301之后,整体控制部310使闸阀G关闭,利用该第2前处理装置150进行PHT处理。
PHT处理结束后,整体控制部310使第2前处理装置150的闸阀G打开,利用输送机构306从第2前处理装置150取出基板W而向真空输送室301输送。在输送机构306的输送臂退避到真空输送室301之后,整体控制部310使第2前处理装置150的闸阀G关闭。
整体控制部310使金属膜成膜装置200的闸阀G打开,将由输送机构306保持着的基板W向该金属膜成膜装置200送入。在输送机构306的输送臂退避到真空输送室301之后,整体控制部310使闸阀G关闭,利用该金属膜成膜装置200进行金属膜成膜处理。在金属膜成膜处理中,进行钨膜406的成膜。由此,金属膜能够以沟槽403的底部的硅为起点而从底部选择性地形成钨膜406。
金属膜成膜处理结束后,整体控制部310使金属膜成膜装置200的闸阀G打开,利用输送机构306从金属膜成膜装置200取出基板W而向真空输送室301输送。在输送机构306的输送臂退避到真空输送室301之后,整体控制部310使金属膜成膜装置200的闸阀G关闭。
整体控制部310使任一个加载互锁室302的闸阀G1打开,将由输送机构306保持着的基板W向该加载互锁室302送入。在输送机构306的输送臂退避到真空输送室301之后,整体控制部310使闸阀G1关闭,使加载互锁室302内恢复成大气气氛。
在加载互锁室302成为预定的大气气氛的时间点,整体控制部310使加载互锁室302的闸阀G2打开,利用输送机构308从加载互锁室302取出基板W而向大气输送室303输送。在输送机构308的输送臂退避到大气输送室303之后,整体控制部310使加载互锁室302的闸阀G2关闭。另外,整体控制部310使由输送机构308保持着的基板W返回载体C。
如此,根据本实施方式的群集系统300,在利用第1前处理装置100和第2前处理装置150对基板W实施了作为前处理的氧化膜去除处理之后,维持真空气氛的状态(不破坏真空)从第2前处理装置150向金属膜成膜装置200输送,能够利用金属膜成膜装置200对实施了氧化膜去除处理的基板W实施金属膜成膜处理。由此,能够在基板W形成低电阻的钨膜406。
<金属膜成膜装置200>
接着,使用图2而对金属膜成膜装置200的构造的一个例子进行说明。图2是本实施方式的群集系统300所具备的金属膜成膜装置200的截面示意图的一个例子。
如图2所示,金属膜成膜装置200具有:处理容器1、基板载置台2、喷头3、排气部4、处理气体供给机构5以及控制装置6。
处理容器1由铝等金属形成,具有大致圆筒状。在处理容器1的侧壁形成有用于送入或送出基板W的送入送出口11,送入送出口11能够利用闸阀12开闭。在处理容器1的主体之上设置有截面呈矩形形状的环状的排气管道13。在排气管道13沿着内周面形成有狭缝13a。另外,在排气管道13的外壁形成有排气口13b。在排气管道13的上表面以封堵处理容器1的上部开口的方式设置有顶壁14。在顶壁14与排气管道13之间利用密封圈15气密地密封。
基板载置台2在处理容器1内将基板W水平地支承。基板载置台2呈与基板W相对应的大小的圆板状,支承于支承构件23。基板载置台2由氮化铝(AlN)等陶瓷材料、铝、镍基合金等金属材料形成,在内部埋入有用于加热基板W的加热器21。加热器21被从加热器电源(未图示)供电而发热。并且,根据设置到基板载置台2的上表面的基板载置面附近的热电偶(未图示)的温度信号来控制加热器21的输出,从而将基板W控制成预定的温度。
在基板载置台2以覆盖基板载置面的外周区域和基板载置台2的侧面的方式设置有由氧化铝等陶瓷形成的罩构件22。
支承构件23从基板载置台2的底面中央贯穿在处理容器1的底壁形成的孔部而向处理容器1的下方延伸,其下端与升降机构24连接。基板载置台2利用升降机构24并借助支承构件23而能够在图1所示的处理位置与该处理位置的下方的以双点划线表示的可进行基板的输送的输送位置之间升降。另外,在支承构件23的处理容器1的下方安装有凸缘部25,在处理容器1的底面与凸缘部25之间设置有波纹管26,该波纹管26将处理容器1内的气氛与外部空气划分开,并随着基板载置台2的升降动作而伸缩。
在处理容器1的底面附近以从升降板27a向上方突出的方式设置有3根(仅图示两根)基板支承销27。基板支承销27能够利用设置到处理容器1的下方的升降机构28并借助升降板27a升降,并能够贯穿被设置到位于输送位置的基板载置台2的贯通孔2a而相对于基板载置台2的上表面突出没入。通过如此使基板支承销27升降,在基板输送机构(未图示)与基板载置台2之间进行基板W的交接。
喷头3向处理容器1内呈喷淋状供给处理气体。喷头3是金属制的,以与基板载置台2相对的方式设置,具有与基板载置台2的直径大致相同的直径。喷头3具有:主体部31,其固定到处理容器1的顶壁14;和喷淋板32,其与主体部31的下方连接起来。在主体部31与喷淋板32之间形成有气体扩散空间33,在气体扩散空间33以贯穿主体部31和处理容器1的顶壁14的中央的方式设置有气体导入孔36。在喷淋板32的周缘部形成有向下方突出的环状突起部34,在喷淋板32的环状突起部34的内侧的平坦面形成有气体喷出孔35。
在基板载置台2存在于处理位置的状态下,在喷淋板32与基板载置台2之间形成处理空间37,环状突起部34与基板载置台2的罩构件22的上表面接近而形成环状间隙38。
排气部4自处理容器1的内部进行排气。排气部4具备:排气配管41,其与排气管道13的排气口13b连接起来;和排气机构42,其与排气配管41连接起来,并具有真空泵、压力控制阀等。在进行处理之际,处理容器1内的气体经由狭缝13a到达排气管道13,而被排气部4的排气机构42从排气管道13经由排气配管41排气。
处理气体供给机构5具有:原料气体供给管线L1、含氢气体供给管线L2、第1连续N2气体供给管线L3、第2连续N2气体供给管线L4、第1快速吹扫管线L5、第2快速吹扫管线L6以及连续含氢气体供给管线L7。
原料气体供给管线L1从作为含金属气体、例如WCl6气体的供给源的原料气体供给源GS1延伸,与汇合配管L8连接。汇合配管L8与气体导入孔36连接。在原料气体供给管线L1,从原料气体供给源GS1侧依次设置有质量流量控制器M1、缓冲罐T1以及开闭阀V1。质量流量控制器M1控制在原料气体供给管线L1流动的WCl6气体的流量。缓冲罐T1暂时积存WCl6气体,在短时间内供给所需要的WCl6气体。开闭阀V1在原子层堆积(ALD:Atomic LayerDeposition)工艺之际切换WCl6气体的供给、停止。此外,WCl6在常温下是固体,在成膜原料罐(未图示)内氯化钨即WCl6作为固体被收纳。在成膜原料罐的周围设置有加热器,将成膜原料罐内的WCl6加热到适当的温度而使WCl6升华,从而作为原料气体供给源GS1向下游侧输送。
含氢气体供给管线L2从作为含氢气体、例如H2气体的供给源的含氢气体供给源GS2延伸,与汇合配管L8连接。在含氢气体供给管线L2,从含氢气体供给源GS2侧依次设置有质量流量控制器M2、缓冲罐T2以及开闭阀V2。质量流量控制器M2控制在含氢气体供给管线L2流动的H2气体的流量。缓冲罐T2暂时积存H2气体,在短时间内供给所需要的H2气体。开闭阀V2在ALD工艺之际切换H2气体的供给、停止。
第1连续N2气体供给管线L3从作为N2气体的供给源的N2气体供给源GS3延伸,与原料气体供给管线L1连接。由此,经由第1连续N2气体供给管线L3向原料气体供给管线L1侧供给N2气体。第1连续N2气体供给管线L3在基于ALD法的成膜中始终供给N2气体,该N2气体作为WCl6气体的载气发挥功能,也具有作为吹扫气体的功能。在第1连续N2气体供给管线L3,从N2气体供给源GS3侧依次设置有质量流量控制器M3、开闭阀V3以及节流孔F3。质量流量控制器M3控制在第1连续N2气体供给管线L3流动的N2气体的流量。节流孔F3抑制由缓冲罐T1、T5供给的比较大的流量的气体向第1连续N2气体供给管线L3倒流。
第2连续N2气体供给管线L4从作为N2气体的供给源的N2气体供给源GS4延伸,与含氢气体供给管线L2连接。由此,经由第2连续N2气体供给管线L4向含氢气体供给管线L2侧供给N2气体。第2连续N2气体供给管线L4在基于ALD法的成膜中始终供给N2气体,该N2气体作为H2气体的载气发挥功能,并且也具有作为吹扫气体的功能。在第2连续N2气体供给管线L4,从N2气体供给源GS4侧依次设置有质量流量控制器M4、开闭阀V4以及节流孔F4。质量流量控制器M4控制在第2连续N2气体供给管线L4流动的N2气体的流量。节流孔F4抑制由缓冲罐T2、T6供给的比较大的流量的气体向第2连续N2气体供给管线L4倒流。
第1快速吹扫管线L5从作为N2气体的供给源的N2气体供给源GS5延伸,与第1连续N2气体供给管线L3连接。由此,经由第1快速吹扫管线L5和第1连续N2气体供给管线L3向原料气体供给管线L1侧供给N2气体。第1快速吹扫管线L5在基于ALD法的成膜中的仅吹扫步骤时供给N2气体。在第1快速吹扫管线L5,从N2气体供给源GS5侧依次设置有质量流量控制器M5、缓冲罐T5以及开闭阀V5。质量流量控制器M5控制在第1快速吹扫管线L5流动的N2气体的流量。缓冲罐T5暂时积存N2气体,在短时间内供给所需要的N2气体。开闭阀V5在ALD工艺的吹扫之际切换N2气体的供给、停止。
第2快速吹扫管线L6从作为N2气体的供给源的N2气体供给源GS6延伸,与第2连续N2气体供给管线L4连接。由此,经由第2快速吹扫管线L6和第2连续N2气体供给管线L4向含氢气体供给管线L2侧供给N2气体。第2快速吹扫管线L6在基于ALD法的成膜中的仅吹扫步骤时供给N2气体。在第2快速吹扫管线L6,从N2气体供给源GS6侧依次设置有质量流量控制器M6、缓冲罐T6以及开闭阀V6。质量流量控制器M6控制在第2快速吹扫管线L6流动的N2气体的流量。缓冲罐T6暂时积存N2气体,在短时间内供给所需要的N2气体。开闭阀V6在ALD工艺的吹扫之际切换N2气体的供给、停止。
连续含氢气体供给管线L7从作为含氢气体、例如H2气体的供给源的含氢气体供给源GS7延伸,与含氢气体供给管线L2连接。由此,经由连续含氢气体供给管线L7向含氢气体供给管线L2侧供给H2气体。连续含氢气体供给管线L7在基于ALD法的成膜中始终供给H2气体。在连续含氢气体供给管线L7,从含氢气体供给源GS7侧依次设置有质量流量控制器M7和开闭阀V7。质量流量控制器M7控制在连续含氢气体供给管线L7流动的H2气体的流量。
控制装置6控制金属膜成膜装置200的各部的动作。控制装置6具有:CPU(中央处理单元:Central Processing Unit)、ROM(只读存储器:Read Only Memory)以及RAM(随机存取存储器:Random Access Memory)。CPU按照储存到RAM等存储区域的制程,来执行所期望的处理。在制程中设定有与工艺条件相对应的装置的控制信息。控制信息可以是例如气体流量、压力、温度、工艺时间。此外,制程和控制装置6所使用的程序也可以存储于例如硬盘、半导体存储器。另外,制程等也可以在收纳到能够由CD-ROM、DVD等移动性的计算机读取的存储介质的状态下被装载于预定的位置而被读出。
<由群集系统300进行的成膜方法>
接着,使用图3~图5来说明由本实施方式的群集系统300进行的成膜方法。图3是表示由本实施方式的群集系统300进行的成膜方法的一个例子的流程图。图4是表示各工序中的基板W的状态的截面示意图。
在步骤S101中,准备基板W。如图4的(a)所示,对于基板W,在硅基体401形成有绝缘膜402,在绝缘膜402形成有沟槽403作为预定图案。在沟槽403的底部的硅部分形成有自然氧化膜404。此外,绝缘膜402主要由SiO2膜构成,但一部分也可以是SiN膜。基板W收纳于例如大气气氛的载体C。基板W被输送机构306、308从载体C经由大气输送室303、加载互锁室302、真空输送室301向第1前处理装置100输送。
在步骤S102中,整体控制部310执行作为化学蚀刻的一个例子的COR处理。此外,化学蚀刻是不使用等离子体的由反应性气体进行的蚀刻,且是各向同性的蚀刻。因此,能够去除具有复杂的形状的沟槽403的底部的自然氧化膜404。作为化学蚀刻,使用NH3气体和HF气体作为化学气体的COR处理较适合。
如图4的(b)所示,在COR处理后,在绝缘膜402的上表面和沟槽403的底部由于NH3气体与HF气体之间的反应而形成主要由六氟硅酸铵((NH4)2SiF6;AFS)构成的反应生成物405。
在COR处理后,基板W被输送机构308从第1前处理装置100经由真空输送室301向第2前处理装置150输送。
在步骤S103中,整体控制部310执行PHT处理。PHT处理是使在步骤S102的COR处理中所生成的反应生成物405升华而将其去除的处理。具体而言,在氮气气氛中,在反应生成物405升华的温度下处理特定的时间,使反应生成物405升华而从基板W去除。由此,如图4的(c)所示,沟槽403的底部的自然氧化膜404(参照图4的(a))被去除。
PHT处理后,基板W被输送机构308从第2前处理装置150经由真空输送室301向金属膜成膜装置200输送。
在步骤S104中,整体控制部310执行使钨膜406成膜的成膜处理。在此,在自然氧化膜被去除了的沟槽403的底部的硅层上,如以下的反应式所示,发生由Si的还原反应导致的原料WClx的分解反应。此外,对于原料WClx,x=3~6。例如,x=6的情况的反应式如以下这样。
2WCl6+5Si→2WSi+3SiCl4
另外,在使用含氟气体而去除了自然氧化膜的情况下,Si表面被氟封锁,在基板表面形成Si-F键。若向该表面供给WClx等含有Cl的金属原料,则氟从被氟封锁的Si表面脱离,金属材料的卤素被置换成氟而使氟被去除。在Si表面,由于氟脱离了而形成供原料吸附的位点,因此,能够使金属膜直接在Si表面生长。这样的在被氟封锁着的表面的反应并不限于WClx,即使使用由Ta、Co、Ni、Mo、Hf、Zr等金属原子与Cl、Br、I等卤素的组合形成的金属原料,也能够实现。对于由使用了HF气体和NH3气体的COR处理作为Si表面的前处理形成的F封锁,如上述那样记载,但并不限于此。例如,也可以是H封锁、Cl(卤)封锁、无(Si)封锁,只要使自然氧化膜被去除即可。
由此,如图4的(d)所示,能够以沟槽403的底部的硅层为起点而直接将钨膜埋入。
在此,列举利用ALD工艺在基板W之上形成钨膜的情况为例而对金属膜成膜装置200的成膜处理进行说明。图5是表示ALD工艺的气体供给序列的一个例子的图。此外,在图5中,将向处理空间37供给气体的情况以涂黑箭头表示,将向缓冲罐填充气体的情况以涂白箭头表示。
首先,向处理容器1内送入基板W。具体而言,在使基板载置台2下降到输送位置的状态下使闸阀12打开。接下来,利用输送臂(未图示)将基板W经由送入送出口11向处理容器1内送入,载置于由加热器21加热到预定温度(例如300℃~600℃)的基板载置台2之上。接下来,使基板载置台2上升到处理位置,使处理容器1内减压到预定的真空度。之后,使开闭阀V3、V4打开,使开闭阀V1、V2、V5、V6、V7关闭。由此,从N2气体供给源GS3、GS4经由第1连续N2气体供给管线L3和第2连续N2气体供给管线L4向处理容器1内供给N2气体而使压力上升,使基板载置台2之上的基板W的温度稳定。此时,从原料气体供给源GS1向缓冲罐T1内供给WCl6气体,缓冲罐T1内的压力被维持为大致恒定。另外,从N2气体供给源GS5、GS6向缓冲罐T5、T6内供给N2气体,缓冲罐T5、T6内的压力被维持为大致恒定。
接下来,利用使用了WCl6气体和H2气体的ALD工艺使钨膜成膜。
图5所示的ALD工艺是使供给WCl6气体的工序S501、供给N2气体的工序S502、供给H2气体的工序S503以及供给N2气体的工序S504反复进行预定循环、交替地供给WCl6气体和H2气体而在基板W之上形成所期望的膜厚的钨膜的工艺。此外,在图5中,仅表示1个循环。
供给WCl6气体的工序S501是向处理空间37供给WCl6气体的工序。在供给WCl6气体的工序S501中,首先,在使开闭阀V3、V4打开着的状态下,从N2气体供给源GS3、GS4经由第1连续N2气体供给管线L3和第2连续N2气体供给管线L4持续地供给N2气体(连续N2气体)。另外,通过使开闭阀V1打开,从原料气体供给源GS1经由原料气体供给管线L1向处理容器1内的处理空间37供给WCl6气体。此时,WCl6气体在暂且积存到缓冲罐T1之后向处理容器1内供给。另外,通过使开闭阀V7打开,来向处理空间37供给H2气体。在供给WCl6气体的工序501中,与WCl6气体同时供给还原气体,从而使所供给的WCl6气体活性化,易于发生之后的供给H2气体的工序503之际的成膜反应。因此,能够维持较高的阶梯覆盖率、且增厚每1个循环的堆积膜厚而增大成膜速度。作为添加的还原气体的流量,能够设为在供给WCl6气体的工序501中不发生CVD反应的程度的流量。
供给N2气体的工序S502是对处理空间37的剩余的WCl6气体等进行吹扫的工序。在供给N2气体的工序S502中,在继续经由第1连续N2气体供给管线L3和第2连续N2气体供给管线L4的N2气体(连续N2气体)的供给的状态下,使开闭阀V1关闭而使WCl6气体的供给停止。另外,使开闭阀V5、V6打开。由此,从N2气体供给源GS5、GS6经由第1快速吹扫管线L5和第2快速吹扫管线L6向处理容器1内的处理空间37供给N2气体。此时,N2气体在暂且积存到缓冲罐T5、T6之后向处理容器1内供给,因此,能够供给比较大的流量。由此,对处理空间37的剩余的WCl6气体等进行吹扫。
供给H2气体的工序S503是向处理空间37供给H2气体的工序。在供给H2气体的工序S503中,在继续经由第1连续N2气体供给管线L3和第2连续N2气体供给管线L4的N2气体(连续N2气体)的供给的状态下,使开闭阀V2打开。由此,从含氢气体供给源GS2经由含氢气体供给管线L2向处理空间37供给H2气体。此时,H2气体在暂且积存到缓冲罐T2之后向处理容器1内供给。利用供给H2气体的工序S503,吸附到基板W上的WCl6被还原。此时的H2气体的流量能够设为使还原反应充分地发生的量。此外,由连续含氢气体供给管线L7向处理空间37供给的H2气体的流量比由含氢气体供给管线L2向处理空间37供给的H2气体的流量小。
供给N2气体的工序S504是对处理空间37的剩余的H2气体进行吹扫的工序。在供给N2气体的工序S504中,在继续经由第1连续N2气体供给管线L3和第2连续N2气体供给管线L4的N2气体(连续N2气体)的供给的状态下,使开闭阀V2关闭而使H2气体的供给停止。另外,使开闭阀V5、V6打开。由此,从N2气体供给源GS5、GS6经由第1快速吹扫管线L5和第2快速吹扫管线L6向处理容器1内的处理空间37供给N2气体。此时,N2气体在暂且积存到缓冲罐T5、T6之后向处理容器1内供给,因此,能够供给比较大的流量。由此,对处理空间37的剩余的H2气体等进行吹扫。
反复进行以上的循环,从而能够向沟槽403内埋入钨。
在此,以下表示金属膜成膜装置200的成膜处理的工艺条件的一个例子。此外,在圆括弧内表示优选的条件范围。
基板温度:480℃(300℃~600℃)
管线L1 WCl6:4.5sccm(1sccm~30sccm)
管线L2 H2:5000sccm(1000sccm~15000Sccm)
管线L7H2:100sccm(1sccm~500Sccm)
管线L5和L6N2:2000sccm(500sccm~5000sccm)
管线L3和L4 N2:800sccm(100sccm~5000sccm)
处理空间压力:45Torr(10Torr~100Torr)
WCl6供给时间[S501]/N2吹扫时间[S502]/H2供给时间[S503]/N2吹扫时间[S504]:0.3秒/0.2秒/0.3秒/0.2秒(各步骤:0.01秒~1秒)
反复次数:50次(根据膜厚而变动,例如,在70A左右时,1次~300次)
接着,针对金属膜成膜装置200的成膜处理,确认了温度依赖性。
能够确认到:在将基板W的温度设为第1温度(例如460℃)的情况下,钨膜不在基板W成膜,在将基板W的温度设为比第1温度高的第2温度(例如480℃)的情况下,钨膜在基板W成膜。另外,能够确认到:在将基板W的温度设为比第2温度高的第3温度(例如500℃)的情况下,在基板W进行成膜的钨膜的膜厚增加。即,能够确认到:通过控制基板W的温度,能够控制钨膜的成膜。
接着,对参考例的群集系统进行说明。参考例的群集系统具有使作为基底膜的TiN膜成膜的基底膜成膜装置和在基底膜之上使钨膜成膜的金属膜成膜装置来替代在本实施方式的群集系统(参照图1)中作为前处理的第1前处理装置(COR处理)和第2前处理装置(PHT处理)。图6是表示由参考例的群集系统进行的成膜方法的各工序中的基板W的状态的截面示意图。
首先,如图6的(a)所示,准备基板W。接着,对于基底膜成膜装置,如图6的(b)所示,作为基底膜407,例如,使TiN膜以沿着凹部的方式使该TiN膜成膜。接着,对于金属膜成膜装置,如图6的(c)所示,在TiN膜之上使钨膜408成膜。此外,对于钨膜408的成膜方法,与本实施方式的钨膜的形成方法同样。
接着,一边与参考例的群集系统的成膜方法对比,一边对本实施方式的群集系统的成膜方法进行说明。
根据本实施方式的群集系统的处理方法,与参考例的群集系统相比较,能够无需基底膜成膜装置。
另外,在第1前处理装置100、第2前处理装置150的前处理的时间比基底膜成膜装置的基底膜(TiN膜)的成膜时间短的情况下,能够使本实施方式的群集系统的处理方法的生产率提高。
图7是表示参考例中的基底膜407和钨膜408的膜厚、与电阻之间的关系的图表。如图7所示,在将基底膜407和钨膜408的膜厚的合计设为恒定(其中,为6nm)的情况下,基底膜407的膜厚越薄,电阻也越小。相对于此,根据本实施方式,由于能够无需基底膜407,因此,与参考例相比较,能够减小电阻。
另外,参考例中的钨膜408的覆盖率依赖于基底膜407的状态。相对于此,根据本实施方式,由于能够无需基底膜407,因此,与参考例相比较,能够使覆盖率提高。
另外,参考例中的钨膜408的晶圆面内均匀性依赖于基底膜407的状态。相对于此,根据本实施方式,由于能够无需基底膜407,因此,与参考例相比较,能够使晶圆面内均匀性提高。
另外,在参考例中,在使钨膜408成膜之际,若基底膜407被用于使钨膜408成膜的原料气体(WCl6)全部蚀刻,则无法使钨膜408成膜。相对于此,根据本实施方式,即使不使用基底膜407,也能够使钨膜406成膜。
图8是对比本实施方式的成膜速率和参考例的成膜速率的图表。如图8所示,在本实施方式中所示的成膜速率比参考例的成膜速率上升了20%。由此,能够使本实施方式的群集系统的处理方法的生产率提高。
另外,在参考例中,钨膜408从形成有基底膜407的沟槽403的侧面和底面进行成膜。相对于此,在本实施方式的群集系统的处理方法中,由于钨膜406不在SiO2上成膜,因此,从沟槽403的底面进行成膜。由此,在本实施方式中,能够使钨膜406从沟槽403的底面选择性地成膜。
以上,对群集系统300的实施方式等进行了说明,但本公开并不限定于上述实施方式等,能够在权利要求书所记载的本公开的主旨的范围内进行各种变形、改良。
如图2和图5所示,说明了金属膜成膜装置200是利用ALD工艺使钨膜成膜的ALD装置,但并不限于此,也可以是CVD装置。
说明了原料气体是WCl6,但并不限于此,也可以是氯化钨,例如WCl5、WCl4、WCl3中的任一者。另外,说明了还原气体是H2,但并不限于此。
说明了本实施方式的成膜系统是具备多个腔室的群集系统300,但并不限于此,也可以是能够在1个腔室中进行前处理和成膜处理的成膜系统。另外,说明了进行COR处理的第1前处理装置100和进行PHT处理的第2前处理装置150构成为不同的处理装置,但并不限于此,也可以构成为利用同样的处理装置进行COR处理和PHT处理。

Claims (12)

1.一种基板处理方法,其中,
该基板处理方法具备如下工序:
准备在表面形成有自然氧化膜的基板的工序;
实施作为去除所述自然氧化膜的处理的前处理的工序;以及
将载置所述基板的载物台的温度加热到预定的温度,向实施了所述前处理之后的所述基板供给氯化钨气体和还原气体而在所述基板直接使钨膜成膜的工序,
其中,在所述使钨膜成膜的工序中,交替地进行同时供给所述氯化钨气体和所述还原气体的工序和在不供给所述氯化钨气体的情况下供给所述还原气体的工序,其中,所述氯化钨是WCl6、WCl5、WCl4以及WCl3中的任一者,
其中,实施前处理的工序包括:
使所述基板暴露于含氮气体与含氟气体的混合气体的第1前处理工序;
通过升华来去除在所述第1前处理工序中产生的副生成物的第2前处理工序,其中,所述副生成物是在所述第1前处理工序中所述自然氧化膜与含氮气体和含氟气体的所述混合气体进行反应而形成的。
2.根据权利要求1所述的基板处理方法,其中,
在所述使钨膜成膜的工序中,控制所述载物台的温度而在所述基板选择性地使所述钨膜成膜。
3.根据权利要求1所述的基板处理方法,其中,
所述第1前处理工序是利用蚀刻去除所述自然氧化膜的蚀刻处理。
4.根据权利要求3所述的基板处理方法,其中,
所述蚀刻处理是不使用等离子体的蚀刻处理。
5.根据权利要求1~4中任一项所述的基板处理方法,其中,
所述还原气体是含有氢的气体。
6.根据权利要求5所述的基板处理方法,其中,
所述含有氢的气体是H2
7.根据权利要求1~4中任一项所述的基板处理方法,其中,
所述实施前处理的工序和所述使钨膜成膜的工序不暴露于大气地进行处理。
8.根据权利要求1~4中任一项所述的基板处理方法,其中,
所述使钨膜成膜的工序中的基板的温度是300℃~600℃。
9.一种成膜系统,其中,
该成膜系统具备:
1个或多个处理装置;以及
控制部,
所述控制部控制所述处理装置,以进行如下工序:
准备在表面形成有自然氧化膜的基板的工序;
实施作为去除所述自然氧化膜的处理的前处理的工序;以及
将载置所述基板的载物台的温度加热到预定的温度,向实施了所述前处理之后的所述基板供给氯化钨气体和还原气体而在所述基板直接使钨膜成膜的工序,
其中,在所述使钨膜成膜的工序中,交替地进行同时供给所述氯化钨气体和所述还原气体的工序和在不供给所述氯化钨气体的情况下供给所述还原气体的工序,其中,所述氯化钨是WCl6、WCl5、WCl4以及WCl3中的任一者,
其中,实施前处理的工序包括:
使所述基板暴露于含氮气体与含氟气体的混合气体的第1前处理工序;
通过升华来去除在所述第1前处理工序中产生的副生成物的第2前处理工序,其中,所述副生成物是在所述第1前处理工序中所述自然氧化膜与含氮气体和含氟气体的所述混合气体进行反应而形成的。
10.根据权利要求9所述的成膜系统,其中,
利用第1处理装置进行所述第1前处理工序,利用第2处理装置进行所述第2前处理工序。
11.根据权利要求9所述的成膜系统,其中,
利用同样的处理装置进行所述第1前处理工序和所述第2前处理工序。
12.根据权利要求9~11中任一项所述的成膜系统,其中,
所述实施前处理的工序和所述使钨膜成膜的工序不破坏真空地进行。
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