CN107438892A - 等离子处理方法以及等离子处理装置 - Google Patents

等离子处理方法以及等离子处理装置 Download PDF

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CN107438892A
CN107438892A CN201780000763.8A CN201780000763A CN107438892A CN 107438892 A CN107438892 A CN 107438892A CN 201780000763 A CN201780000763 A CN 201780000763A CN 107438892 A CN107438892 A CN 107438892A
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gas
plasma
processing method
amorphous carbon
film
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CN107438892B (zh
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寺仓聪志
森政士
荒濑高男
岩濑拓
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Hitachi Ltd
Hitachi High Tech Corp
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Abstract

本发明提供等离子处理方法及其处理装置，在对使用了含硼的无定形碳膜的层叠膜进行蚀刻时，通过实现高选择比、高蚀刻速率而能够进行连贯加工，通过简化掩模成膜工序来实现包括前后工序在内的高处理量化，进而具有垂直加工的形状控制性。本发明是通过对具有含硼的无定形碳膜的层叠膜进行等离子蚀刻来形成掩模的等离子处理方法，其特征在于，使用氧气、含氟气体、卤素气体和四氟化硅气体的混合气体或者氧气、含氟气体、卤素气体和四氯化硅气体的混合气体来对所述含硼的无定形碳膜进行等离子蚀刻。

Description

等离子处理方法以及等离子处理装置
技术领域
本发明涉及使用与半导体制造相关的等离子来对样品进行处理的等离子处理方法及其装置。
背景技术
在具有三维结构的闪速存储器(3D-NAND等)的栅极制造工序中，伴随着器件的大容量化，如专利文献1公开的那样，多晶硅膜与硅氧化膜的配对层总数不断增加到48层、72层、96层、120层，等离子蚀刻加工的高纵横比化正在进展中。
过去以来，在对这些层叠膜进行蚀刻时，将图案形成后的光致抗蚀剂膜(PR)、防反射膜(Bottom Anti-Reflection Coat：BARC)和无定形碳膜(Amorphous Carbon Layer：ACL，以下称作ACL膜)的层叠膜作为蚀刻掩模来使用，但是伴随着高纵横比化，无定形碳膜的掩模的厚度不足逐渐明显化了。
因此，在ACL膜中掺杂(含有)硼元素(B)，采用含有使耐等离子性得到提升的硼的B-Doped ACL膜。在对现有的ACL膜进行蚀刻时，以氧为主体，使用添加了COS、氮或者用氩、氦稀释了的等离子来将抗蚀剂的图案转印到ACL膜，但是很难用该气体系列对含有10到40％程度的硼的B-Doped ACL膜进行蚀刻。
为了解决该问题，在专利文献2中公开了通过使晶片台的温度成为100℃以上从而增加硼的反应生成物的挥发性来进行蚀刻的方式，并且在专利文献3中公开了如下方法：通过使用CH4、Cl2、SF6、O2的混合气体形成氟化硼来增加反应生成物挥发性，并且用Cl2、CH4来控制加工垂直性，由此在10～30℃的常温下进行蚀刻。
现有技术文献
专利文献
专利文献1：JP特开2015-144158号公报
专利文献2：JP特开2014-007370号公报
专利文献3：US2015/0064914 A1
发明内容
发明要解决的课题
在专利文献2公开的方法中，在对PR/BARC/SiON/B-doped ACL的掩模结构的样本进行蚀刻时，光致抗蚀剂膜由于高温而碳化，从而图案会受损。另外，由于在下层的硅/硅氧化膜的配对层的蚀刻时需要在50℃以下的低温侧进行蚀刻，因此不能在同一反应室进行从掩模到基底膜的蚀刻(所谓的连贯处理)。即使进行了连贯处理，也会出现温度等待时间长从而蚀刻处理的处理量降低这样的问题。
另外，在专利文献3公开的方法中，由于与现有的ACL膜的蚀刻时相比，对硅氮氧化膜选择比更小，因此在使用现有的ACL膜蚀刻时所需的30-40nm厚度的硅氮氧化膜的情况下，会出现如下问题：蚀刻不能到达下层的SiO2膜，或者在蚀刻推进中从硅氮氧化膜的开口部之时起产生逐渐后退的刻面(faceting)。
为了避免这些问题而不得不采用加厚硅氮氧化膜的方法，但是掩模成膜工序中的处理量会大幅降低，进而出现使CoO(Cost of Owership)大幅增加的问题。
进一步地，由于存在按照与上下层膜的组合来适当变更硼浓度或所使用的台温度的中心值的可能性，因此在进行B-Doped ACL膜的蚀刻时，需要具有能消除其他形状异常(侧蚀、弯曲(bowing)、蚀刻停止)的形状控制性而能够实现接近于垂直的蚀刻加工。
以上，本发明的目的在于，提供一种等离子处理方法及其处理装置，在对使用了含硼的无定形碳膜的层叠膜进行蚀刻时，通过实现高选择比、高蚀刻速率而能够进行连贯加工，通过简化掩模成膜工序来实现包括前后工序在内的高处理量化，进而具有垂直加工的形状控制性。
用于解决课题的手段
本发明的等离子处理方法通过对具有含硼的无定形碳膜的层叠膜进行等离子蚀刻来形成掩模，所述等离子处理方法的特征在于，使用氧气、含氟气体、卤素气体和四氟化硅气体的混合气体或者氧气、含氟气体、卤素气体和四氯化硅气体的混合气体来对所述含硼的无定形碳膜进行等离子蚀刻。
另外，本发明的等离子处理装置具备：对样品进行等离子处理的处理室；和供给用于在所述处理室内生成等离子的高频功率的高频电源，所述等离子处理装置的特征在于，还具备：将第一气体和向所述第一气体混合的气体即第二气体经由多个区域供给到所述处理室内的气体供给机构。
发明效果
根据本发明，能将无机膜作为掩模，以高蚀刻速率且以高选择比对含硼的无定形碳膜进行蚀刻。
附图说明
图1是本发明所涉及的平行平板型的有磁场VHF干式蚀刻装置的纵截面图。
图2是表示本发明的等离子处理方法的1个实施例中的蚀刻形状的图。
图3是表示形状异常的蚀刻截面的示意图。
图4是表示相对于本发明中的B-Doped ACL蚀刻速率以及掩模选择比的偏置功率依赖性的图。
图5是表示相对于本发明中的B-Doped ACL蚀刻速率以及掩模选择比的压力依赖性的图。
具体实施方式
以下，用图1到图5来说明本发明的实施例。图1是作为本发明的等离子处理装置的一例的平行平板型的有磁场VHF干式蚀刻装置的纵截面图。
在具有圆筒状的内部空间且作为处理室的真空容器101内的下部设置有在上表面载置作为样品的晶片102的样品台103。在样品台103经由第一匹配器104连接有偏置施加用的高频电源105以及晶片静电吸附用的直流电源106。另外，在样品台103连接有调温组件107。高频电源105在该情况下使用频率4MHz。
另外，在真空容器101内的下部设置排气口，省略了图示的排气装置与该排气口相连。在真空容器101内的上部，与样品台103的晶片载置面对置地设置平板状的天线108，并经由第二匹配器109连接等离子生成用的高频电源110。高频电源110在本实施例中使用频率200MHz的VHF波。另外，在真空容器1外部的上表面以及外周设置有在真空容器101内形成磁场的螺线管线圈111。螺线管线圈111在真空容器101的轴方向上形成朝向样品台103的发散磁场。
在与样品台103对置的天线108的下表面设置具有大量气体供给孔的喷淋板112，在天线108与喷淋板112之间形成内侧空间和包围内侧空间的外侧空间，气体供给孔与各个空间相连。在内侧空间设置内侧气体供给路113，在外侧空间设置外侧气体供给路114。在内侧气体供给路113混合连接主气体系统115和内侧添加气体系统116，在外侧气体供给路114混合连接主气体系统115和外侧添加气体系统117。
主气体系统115是由氧、含氟气体、卤素气体和惰性气体构成的混合气体即第一气体的气体系统，在本实施例中，含氟气体是CHF3，卤素气体是Cl2，惰性气体是N2。主气体系统115由如下要素构成：对气体源O2的流量进行控制的流量控制器A118；对气体源CHF3的流量进行控制的流量控制器B119；对气体源Cl2的流量进行控制的流量控制器C120；对气体源N2的流量进行控制的流量控制器D121a；分别与这些流量控制器118到121a连接的断流阀123；和供给经由各个断流阀123而混合的气体的气体分流器124。
内侧添加气体系统116以及外侧添加气体系统117是由含硅气体(四氯化硅气体或四氟化硅气体)和惰性气体构成的混合气体即第二气体的气体系统，在本实施例中，含硅气体是SiCl4，惰性气体是N2。内侧添加气体系统116由对气体源N2的流量进行控制的流量控制器D121b、对气体源SiCl4的流量进行控制的流量控制器E122a、和分别与这些流量控制器121b以及122a连接的断流阀123构成，供给经由各个断流阀123而混合的气体。外侧添加气体系统117由对气体源N2的流量进行控制的流量控制器D121c、对气体源SiCl4的流量进行控制的流量控制器E122b、和分别与这些流量控制器D121c以及122b连接的断流阀123构成，供给经由各个断流阀123而混合的气体。
被流量控制器118到121a将来自各气体源的气体流量调整成各设定流量的各气体由气体流量分流器115以给定的比率进行分流而流到内侧气体供给路113和外侧气体供给路114。被流量控制器121b以及122a将来自各气体源的气体流量调整成各设定流量的各气体与由气体流量分流器115分流向内侧气体供给路113的气体混合，被供给到喷淋板112的内侧空间，并经由气体供给孔供给到真空容器101的中央侧。
被流量控制器121c以及122b将来自各气体源的气体流量调整成各设定流量的各气体与由气体流量分流器115分流向外侧气体供给路114的气体混合，被供给到喷淋板112的外侧空间，并经由气体供给孔供给到包围真空容器101的中央部的外侧。
即，主气体由气体流量分流器124与喷淋板的被分离的内外区域相匹配地以给定的比率进行分割，使分别进行了流量调整的添加气体与以给定比率分割后的各主气体合流，供给到喷淋板的内外区域。由此，能得到在真空容器101内的喷淋板112下方半径方向上对各气体成分进行了任意调整的面内分布。
另外，在本实施例中，将喷淋板112内的气体存贮空间分离成内外的2个区域，但也可以是3个区域以上，另外也可以在圆周方向上分离多个，只要与分离的数目相匹配地设定气体流量分流器124的分割数，并设置同一气体种类的添加气体系统的数目即可。
另外，对于这样的气体区域分割的效果来说，喷淋板112与样品台103的距离越窄则越有效果。
利用上述那样构成的装置如下那样进行处理。
将由省略图示的搬运装置搬入到真空容器101内的晶片102配置在样品台103上，通过来自直流电源106的电压施加而将晶片102静电吸附在样品台103上。对被吸附、保持于样品台103的晶片102的背面供给作为导热气体的H2气体，与由调温组件107进行了温度调整的样品台103之间进行热传递，将晶片102维持在给定的处理温度。
在将晶片102保持于样品台103之后，在真空容器101内，从主气体系统115、内侧添加气体系统116以及外侧添加气体系统117对内侧气体供给路113以及外侧气体供给路114供给分别进行过流量控制的处理气体即O2、CHF3、Cl2、SiCl4、N2的混合气体。被供给的混合气体经由喷淋板112供给到真空容器内，在真空容器101内维持给定的处理压力，与来自高频电源110的200MHz的高频功率一起作用来自螺线管线圈111的磁场，由此混合气体被激发而等离子化。
在生成等离子之后，由高频电源105对样品台103供给偏置用的高频功率。由此，等离子中的离子入射到晶片2，进行晶片102的蚀刻处理。这时，对供给到真空容器101内的各气体成分在半径方向上进行任意调整，调整成：在等离子中，离解的气体成分的自由基和离子按照该面内分布进行分布，均匀地作用于晶片102面内的蚀刻处理。
在此，作为被蚀刻件的晶片102具有图2(a)所示的层叠膜。在晶片基板上设置配对层201，在本实施例中设置将硅氧化膜(SiO2)和多晶硅膜(Poly-Si)交替层叠的层叠膜，在配对层201上依次设置ACL膜(B-Doped ACL膜)202、硅氮氧化膜(SiON)203、防反射膜(BARC)204、光致抗蚀剂膜(PR)205。
接下来，说明上述结构的膜的蚀刻处理。首先，如图2(b)所示那样，将使电路图案曝光的光致抗蚀剂膜205作为掩模，通过蚀刻对防反射膜204、硅氮氧化膜203转印图案。在该硅氮氧化膜203的蚀刻处理中使用CHF3气体和SF6气体的混合气体。另外，这时也可以加进将光致抗蚀剂膜205以及防反射膜204去除的处理。接下来，如图2(c)所示那样，将硅氮氧化膜203作为掩模来对B-doped ACL202进行蚀刻。
在本发明中，由于将硅氮氧化膜203作为掩模来对ACL膜202中的硼进行蚀刻，因此特征在于，除了使用过去作为ACL的蚀刻剂的氧以外，还使用含氟气体、卤素气体和四氯化硅气体(SiCl4)或四氟化硅气体(SiF4)的混合气体。
这时，卤素气体相对于气体整体的比例根据B-Doped ACL202中所含的硼的含有量(例如5-70％)和调温组件107的设定温度来适当设定。在本实施例中，在对55％的硼浓度的B-Doped ACL膜进行蚀刻的情况下，将调温组件107的温度设为50℃，使用O2气体、CHF3气体、Cl2气体和SiCl4气体的混合气体。在该情况下，各气体种类的倾向如以下那样。
首先，若CHF3的比例相对于气体整体的流量较高，则氟自由基的供给变得过剩，与硼的反应自不必说，与碳的反应也得到促进，如图3(a)所示那样，在B-Doped ACL膜202发生侧蚀301或弯曲302。另外，若CHF3的比例低，则蚀刻不推进，如图3(b)所示那样成为蚀刻停止303。并且，通过添加Cl2，并适当控制与CHF3的气体比，从而能兼顾侧蚀抑制和高蚀刻速率。
另外，一般，对于样品台103的温度来说，为了在B-Doped ACL膜的上方的膜到下方的膜的连贯处理中维持高处理量，而优选设定成使在B-Doped ACL膜的上方的膜到下方的膜的蚀刻中合适的各个温度之差成为±10℃以内(在步骤间的变化率为1℃/s的情况下，温度变化等待时间为10s以内)。另外，一般按照B-Doped ACL膜的上方以及下方的层的材质变更来使样品台103的温度进行变化。
因此，在对B-Doped ACL膜的上方的膜到下方的膜进行连贯处理时，根据需要来提高样品台103的温度，在使CHF3的流量比在各个膜处降低、增加的基础上维持高蚀刻速率，进而控制相对于CHF3气体的Cl2气体比率，由此能兼顾高蚀刻速率和垂直性。反之，在使样品台103的温度降低的情况下，由于因温度降低，氟自由基的反应概率降低，从而能使侧蚀减少，因此使相对于CHF3气体的Cl2气体比率降低即可。即，还能通过调整样品台103的温度来调整弯曲形状或锥形形状的角度。
虽然能通过将相对于CHF3气体的Cl2气体比率设定得高来得到各向异性高的形状，但是也能通过使用高偏置功率、高压力区域来进行与现有的ACL蚀刻同等以上的高速率的处理。另外，高偏置化具有由反应生成物的增加带来的侧壁保护增加的效果，且具有抑制成为侧蚀或弯曲形状的效果。进而，如图4所示那样，B-Doped ACL膜的蚀刻速率401在偏置功率为1000W以下的区域中伴随着偏置功率的增加而大幅增加，但是在1000W以上的区域中缓慢地增加。
另外，掩模选择比402虽然伴随着偏置功率的增加而缓慢地减少，但是减少幅度较小。即，为了以高蚀刻速率对B-Doped ACL膜进行处理，优选偏置电源的功率设定设为1000W以上。这时，在4MHz的1000W下，由于正弦波的峰值间电压即Vpp为1350V，因此在偏置频率不同的情况下，能通过进行成为该Vpp以上的电源功率控制、或直接进行Vpp控制来调整。
进一步地，由于高压化会增加自由基流量(radical flux)，降低等离子密度，因此如图5所示那样，伴随着高压化，B-Doped ACL膜的蚀刻速率501增加，选择比也增加。由于选择比502在压力为4Pa以上的区域中饱和，因此压力设定优选为4Pa以上。
并且，在本发明中，由于通过添加四氯化硅气体或四氟化硅气体，从而硅氧化化合物沉积于作为掩模的硅氮氧化膜203，硅氮氧化膜203的蚀刻量减少，因此能增加选择比。另外，由于掩模的残留量增加，因此能减少掩模的后退，能抑制图3(c)所示那样形状的上部的刻面304，能使掩模膜厚成为例如30-40nm这样的现有的ACL蚀刻处理程度的厚度。由此，避免了掩模成膜工序的复杂化，能提升处理量、CoO。
由于能如以上那样通过CHF3气体相对于Cl2气体的比和偏置功率来调整垂直性，因此晶片台为100℃以下即可。但是，为了对B-Doped ACL膜的上方以及下方的层叠膜在1个反应室中进行连贯加工并维持高处理量，优选设为0℃以上60℃以下。
另外，在本实施例中，使用CHF3气体作为含氟气体，但是此外也可以使用CH2F2气体、CH3F气体、NF3气体、CF4气体、SF6气体。另外，除了Cl2气体以外还可以使用含Br气体的HBr气体、HI气体。进而，除了SiCl4气体以外还可以使用SiF4气体。例如，在使用相比CHF3气体产生更多量的氟的NF3气体、CF4气体、SF6气体等的情况下，能通过使氟系气体比相比CHF3气体使用时更降低，或通过降低样品台103的设定温度来维持垂直形状。
进而，在本实施例中是使用氧气、含氟气体、卤素气体和四氯化硅气体的混合气体或者氧气、含氟气体、卤素气体和四氟化硅气体的混合气体来对含硼的无定形碳膜进行等离子蚀刻的示例，但是即使用N2气体、Ar气体、He气体、Xe气体、Kr气体等惰性气体对氧气、含氟气体、卤素气体和四氯化硅气体的混合气体或者氧气、含氟气体、卤素气体和四氟化硅气体的混合气体进行稀释，也能起到与本实施例同等的效果。
另外，在使用HBr气体的情况下，由于反应性比Cl2气体低，因此能以比Cl2气体小的流量来进行调整。在使用SiF4气体时，由于作为氧化膜的前体，同时还作为氟元素的供给源，因此能降低氟系气体的量，并且能通过适当调整流量来实现高选择比。
另外，在本实施例中是含硼的无定形碳膜即B-Doped ACL膜的掩模形成例，但是将本发明所涉及的干式蚀刻应用在不含硼的无定形碳膜中也能得到与本实施例同等的效果。即，将本发明所涉及的干式蚀刻应用在现有的无定形碳膜中也能得到与本实施例同等的效果。
这是因为，不含硼的无定形碳膜的主成分是与含硼的无定形碳膜的主成分相同的有机材料，通过添加四氯化硅气体或四氟化硅气体，从而硅氧化化合物沉积于作为掩模的硅氮氧化膜203，硅氮氧化膜203的蚀刻量减少，由此使选择比得到提升。
进而，为了实施本发明所涉及的干式蚀刻方法，需要以下蚀刻装置：即，具备上述的气体种类，且能施加3000W程度的偏置，在4Pa以上的高压力下是均匀的。在本实施例中使用了图1所示的平行平板结构的VHF蚀刻装置，但是在其他的使用Capasitively CoupledPlasma(CCP)、Inductively Coupled Plasma(ICP)、Micro Wave Electron CyclotronResonance(μ波ECR)等其他等离子源的等离子蚀刻装置中，也能通过调整压力、气体流量、气体比、偏置功率、频率、台温度等来得到与本实施例同样的效果。
以上，根据本发明，由于能将无机膜作为掩模以高蚀刻速率且以高选择比对无定形碳膜进行蚀刻，因此能进行包括前后工序在内的连贯蚀刻处理，能实现由简化掩模成膜工序带来的包括前后工序在内的高处理量化。
标号说明
101 真空容器
102 晶片
103 样品台
104 第一匹配器
105 偏置施加用的高频电源
106 直流电源
107 调温组件
108 天线
109 第二匹配器
110 等离子生成用的高频电源
111 螺线管线圈
112 喷淋板
113 内侧气体供给路
114 外侧气体供给路
115 主气体系统
116 内侧添加气体系统
117 外侧添加气体系统
118 流量控制器A
119 流量控制器B
120 流量控制器C
121a 流量控制器D
121b 流量控制器D
121c 流量控制器D
122a 流量控制器E
122b 流量控制器E
123 断流阀
124 气体分流器
201 硅氧化膜与多晶硅膜的配对层
202 B-Doped ACL膜
203 硅氮氧化膜
204 防反射膜
205 光致抗蚀剂膜
301 侧蚀
302 弯曲
303 蚀刻停止
304 刻面

Claims (9)

1.一种等离子处理方法，通过对具有含硼的无定形碳膜的层叠膜进行等离子蚀刻来形成掩模，所述等离子处理方法的特征在于，
使用氧气、含氟气体、卤素气体和四氟化硅气体的混合气体或者氧气、含氟气体、卤素气体和四氯化硅气体的混合气体来对所述含硼的无定形碳膜进行等离子蚀刻。
2.根据权利要求1所述的等离子处理方法，其特征在于，
所述含氟气体是CHF3气体、CH2F2气体、CH3F气体、NF3气体、CF4气体或SF6气体，
所述卤素气体是Cl2气体、HBr气体或HI气体。
3.根据权利要求1所述的等离子处理方法，其特征在于，
所述卤素气体相对于所述混合气体的流量比率比所述含氟气体相对于所述混合气体的流量比率高。
4.根据权利要求1所述的等离子处理方法，其特征在于，
通过对载置成膜了所述层叠膜的样品的样品台供给1000W以上的高频功率或者对所述样品台施加1350V以上的峰值间高频电压，来对所述含硼的无定形碳膜进行等离子蚀刻。
5.根据权利要求1～4中任一项所述的等离子处理方法，其特征在于，
将压力设为4Pa以上来对所述含硼的无定形碳膜进行等离子蚀刻。
6.根据权利要求1所述的等离子处理方法，其特征在于，
使用O2气体、CHF3气体、Cl2气体和SiCl4气体的混合气体来对所述含硼的无定形碳膜进行等离子蚀刻。
7.一种等离子处理方法，通过对具有无定形碳膜的层叠膜进行等离子蚀刻来形成掩模，所述等离子处理方法的特征在于，
使用氧气、含氟气体、卤素气体和四氟化硅气体的混合气体或者氧气、含氟气体、卤素气体和四氯化硅气体的混合气体来对所述无定形碳膜进行等离子蚀刻。
8.一种等离子处理装置，具备：
对样品进行等离子处理的处理室；和
供给用于在所述处理室内生成等离子的高频功率的高频电源，
所述等离子处理装置的特征在于，还具备：
将第一气体和向所述第一气体混合的气体即第二气体经由多个区域供给到所述处理室内的气体供给机构。
9.根据权利要求8所述的等离子处理装置，其特征在于，
所述气体供给机构具有：
将混合了多种气体的第一气体向所述多个区域的各个区域供给的第一气体配管；和
与所述第一气体配管连接并流过所述第二气体的第二气体配管。
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