CN1757101A - 基板处理方法 - Google Patents

基板处理方法 Download PDF

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CN1757101A
CN1757101A CNA2004800054966A CN200480005496A CN1757101A CN 1757101 A CN1757101 A CN 1757101A CN A2004800054966 A CNA2004800054966 A CN A2004800054966A CN 200480005496 A CN200480005496 A CN 200480005496A CN 1757101 A CN1757101 A CN 1757101A
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plasma
substrate
same
processing method
oxide film
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CN100514573C (zh
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中西敏雄
尾崎成则
佐佐木胜
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Tokyo Electron Ltd
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Abstract

本发明提供一种基板处理方法，由下述过程构成，即，将硅基板表面暴露于惰性气体和氢气的混合气体等离子体中的第一处理过程；以及在所述第一处理过程之后，通过等离子体处理，对所述硅基板表面进行氧化处理、氮化处理以及氮氧化处理的任一处理的第二处理过程，其中，在第一处理过程中，除去残留在基板表面的有机物。

Description

基板处理方法
技术领域
本发明涉及一般的基板处理技术，特别涉及在硅基板上形成绝缘膜的基板处理方法。
在半导体制造技术中，在硅基板上形成绝缘膜的技术是最为基本且重要的技术。特别是对于MOS晶体管的门绝缘膜等，需要非常高质量的绝缘膜。在近阶段的超微细化半导体装置中，随着微细化的发展，门绝缘膜的膜厚减少到1nm左右，需要能够高质量地形成这种薄绝缘膜的技术。
背景技术
目前，如MOS晶体管的门绝缘膜所使用的高质量的氧化硅膜是通过对硅基板表面进行热氧化处理来形成的。在通过这样形成的热氧化硅膜中所含有的悬挂键数量少，即使应用在如门绝缘膜这种施加覆盖信道区域而设置的高电场的绝缘膜的情况下，载体的陷阱很少，能够实现稳定的界限值特性。
另一方面，通过微细化技术的发展，今天，逐渐可以制造出切成1μm门长的超微细化半导体装置。
在这种超微细化半导体装置中，如果要通过缩短门长度来提高半导体装置的动作速度，则需要按照表皮氧化规则减少门绝缘膜的厚度。例如，当门长度为0.1μm的MOS晶体管时，需要将门绝缘膜的厚度减少到2nm以下，但是，在现有热氧化膜中，如果这样减少膜的厚度，则隧道电流产生的门漏电流增大。由此，认为2nm的膜厚是热氧化膜的门绝缘膜的界限。在膜厚为2nm的热氧化膜中，实现了1×10-2A/cm2左右的门漏电流。
与此相对，提出了通过对硅基板进行微波等离子体的氧化处理来形成更高质量的氧化硅膜的技术。
在通过这种硅基板的微波等离子体氧化而形成的氧化硅膜中，甚至在膜厚为1.5nm的情况下，能够确认以1V的施加电压实现了1×10-2A/cm2左右的漏电流。这样，可以认为采用微波等离子体而形成的氧化硅膜，能够突破使用现有热氧化膜的半导体装置中的微细化的界限。另外，通过采用了微波等离子体的基板处理，能够超出热氧化膜的膜质在硅基板上形成电容率大的氮氧化膜或者氮化膜。在用于氮氧化膜或者门绝缘膜的情况下，在换算成氧化硅膜的膜厚为1nm的情况下，当以相同的1V的施加电压进行测定时，实现了1×10-2A/cm2以下的漏电流。
对于通过微波等离子体进行的基板处理来说，典型地，能够以500℃以下的低温来实行，这样，能够缩短升温以及降温基板所需要的时间，从而能够以较高的生产效率来生产半导体装置。此外，在进行这种低温处理时，即使在基板上已经形成扩散区域，在扩散区域中的杂质浓度曲线也不会发生变化，从而能够可靠地实现期望的元件特性。
不过，这样的门绝缘膜需要如下要求，即，第一，漏电流小；第二，高度信赖性。
图1表示的是，关于通过本发明的发明人进行的微波等离子体氧化处理在硅基板表面形成10nm厚度的氧化硅膜(图中以“等离子体氧化膜”表示)，将累积不良率F和达到破坏的积分电荷量(Qbd)之间关系(TDDB特性)，与同样厚度的热氧化膜的情况相比较的情况。其中，纵轴表示的是累积不良率F，横轴表示的是达到绝缘破坏的积分电荷量Qbd。等离子体氧化膜是通过使用后面图2所述的微波等离子体基板处理装置，在氩气和氧气的混合气体等离子体中、以400℃的基板温度来等离子体氧化进行过自然氧化膜除去工序的硅基板表面而形成的。
参照图1，在热氧化膜的情况下，表示累积不良率F的线对于积分电荷量Qbd具有急剧的坡度，从而可知在积分电荷量Qbd达到限定值的情况下产生绝缘破坏。即，这种绝缘膜具有以可预测的寿命为特征的优异的信赖性。
与此相反，对于等离子体氧化膜来说，表示累积不良率F的线的坡度小，表示在各种积分电荷量中，产生绝缘膜的不良。在这样的绝缘膜中，不能预测元件寿命，因此不能获得信赖性。
发明内容
因此，本发明总的目的在于提供一种解决上述问题的新型且实用的基板处理方法。
本发明具体的目的在于提供一种基板处理方法，在通过等离子体中的氧化处理、氮化处理或者氮氧化处理而在硅基板表面上形成氧化膜、氮化膜或者氮氧化膜时，能够提高形成的膜的信赖性，而对于使用这种绝缘膜的半导体装置来说，能够保证较长的元件寿命。
本发明的其他目的在于提供一种基板处理方法，其特征在于，包括：将硅基板表面暴露于惰性气体和氢气的混合气体等离子体中的第一处理过程；以及在所述第一处理过程之后，通过等离子体处理，对所述硅基板表面进行氧化处理、氮化处理以及氮氧化处理中的任何一种处理的第二处理过程。
根据本发明，在通过等离子体进行的基板处理之前，通过将硅基板表面暴露于惰性气体和氢气气体的混合气体等离子体中，能够有效地除去残留在基板表面上的有机物，并在新鲜的硅表面上形成较高质量的绝缘膜。
本发明的其他目的以及特征会从以下参照附图的同时所进行的本发明的详细说明中得到明确。
附图说明
图1是表示现有的热氧化膜以及等离子体氧化膜的TDDB特性图。
图2A、2B是表示本发明所使用的等离子体处理装置的构造图。
图3A、3B是表示根据本发明第一实施方式所进行的基板处理工序图。
图4是表示通过本发明第一实施方式所获得的等离子体氧化膜的TDDB特性图。
图5是表示本发明的第一小时所获得的等离子体氧化膜的漏电流特性图。
图6A、6B是表示根据本发明第二实施方式所进行的基板处理工序图。
具体实施方式
(第一实施方式)
本发明的发明人对通过微波等离子体处理而进行的在硅基板上形成氧化膜、氮化膜、氮氧化膜的过程进行了试验性研究，结果表明，残留在硅基板表面上的有机物对在基板上形成的绝缘膜的信赖性带来很大影响。
图2A、2B是表示本发明的发明人所使用的微波等离子体基板处理装置10的构造图。
参照图2A，微波等离子体基板处理装置10具有处理容器11，其形成有保持被处理基板W的基板保持台12，处理容器11在排气口11A、11B处而被排气。
在上述处理容器11上，对应上述基板保持台12上的被处理基板W而形成有开口部，上述开口部通过由石英或者铝等低损失陶瓷制成的盖板13而封住。而且，在盖板13的下方，以与上述被处理基板W相对的方式而形成有喷淋板14，其形成有气体导入路14A和与其连通的多个喷嘴开口部，由石英或者铝等低损失陶瓷而制成。
上述喷淋板14以及盖板13形成有微波窗，在上述盖板13的外侧形成有放射槽形天线(radial line slot antenna)或者喇叭形天线(hornantenna)等微波天线15。
工作时，上述处理容器11内部的处理空间通过经由上述排气口11A、11B的排气而被设定在特定的处理压力，从所述喷淋板14与氩气或者Kr等惰性气体一起导入氧化气体或者氮化气体。
图2B是表示上述放射槽形天线15的构造图。
参照图2B，上述放射槽形天线15包括经由同轴导波管等而连接在外部微波源的平坦的圆盘形的天线主体，在上述天线主体的开口部设置有放射板15A，如图2B所示，其形成有多个缝隙15a以及与之垂直相交的多个缝隙15b。在上述天线主体和上述放射板15A之间，插入有由厚度一定的电介质板制成的滞相板(未图示)。
而且，通过从上述天线15导入频率为数GHz的微波，而在上述处理容器11中对被处理基板W的表面激励高密度微波等离子体。通过由微波激励等离子体，而在图1的基板处理装置中，使等离子体的电子温度降低，从而能够避免被处理基板W或者处理容器11内壁的损伤。此外，形成的原子团沿着被处理基板W的表面而径向流动，因为迅速地被排气，所以抑制原子团的再结合，从而能够在550℃以下的低温中进行高效率且非常平均的基板处理。
图3A～图3B表示的是本发明的发明人使用图1的基板处理装置10而进行的作为本发明的基础研究的、与本发明第一实施方式对应的基板处理过程。
参照图3A，将通过HF处理而除去了自然氧化膜的硅基板21作为上述被处理基板W而放入上述基板处理装置10的处理容器11中，从上述喷淋板14导入氩气和氢气的混合气体，通过微波对其进行激励来产生等离子体。
对于一个例子来说，将处理容器11内的处理压力设定为7Pa，分别以1000SCCM及40SCCM的流量供给氩气和氢气，在400℃的基板温度中，通过以1500W的功率向上述微波天线15供给频率为2.4GHz的微波，而在上述被处理基板W的表面附近产生高密度等离子体。
在图3A的处理过程中，通过将上述硅基板21的表面暴露于所述等离子体中，残留在基板表面的有机物即使在400℃的较低的基板温度中也会以碳氢化合物的形式而被有效地除去，在基板表面露出新鲜的硅表面。
然后，在图3B的处理过程中，在实施过图3A所示处理的硅基板21上，通过实施下述处理将氧化硅膜22形成为10～1nm的厚度，即，典型地，将所述处理用区域11内的处理压力设定为7Pa，分别以1000SCCM以及40SCCM的流量供给氩气和氧气，在400℃的基板温度时，以1500W的功率向微波天线15供给频率为2.4GHz的微波。
图4表示的是将这样获得的氧化硅膜中的累积不良率F和破坏电荷量Qdb之间关系(TDDB)与图1的结果进行的比较。此外，在图4中还一并表示在图3A的处理过程中将硅基板21暴露于氩等离子体时的结果。其中，在图4中，将上述氧化硅膜形成为10nm的厚度。
参照图4，省略图3A的前处理过程，对在硅基板21上直接将氧化硅膜22形成为10nm的厚度时与图1中说明的等离子体氧化膜对应，但是，在此情况下，如上述图2中所说明的，破坏电荷量Qdb会产生特别大的不均匀。
与此相反，在图3A的前处理过程中，在进行氩等离子体处理的情况下，破坏电荷量Qdb的不均匀会减少，特别是如图3A所示，当在氩气和氢气的混合等离子体中进行上述前处理工程的情况下，破坏电荷量Qbd的不均匀会进一步减少，可获得与热氧化膜的情况相当的结果。即，通过在氩气和氢气的混合气体等离子体中进行图3A的前处理过程，可获得具有与热氧化膜相当的信赖性的等离子体氧化膜。
而且，从图4中可知，本实施例中的等离子体氧化膜的破坏电荷量Qdb的绝对值与热氧化膜的情况相比进一步地增大，表示出获得的等离子体氧化膜的寿命增大。
在图1或者图4中，在氧化气体中、在以高温而形成的热氧化膜中，破坏电荷量Qdb的不均匀减小，在氩气和氧气的混合气体等离子体中，以400℃左右的低温形成的等离子体氧化膜的破坏电荷量Qdb的不均匀增大，该事实表明残留在硅基板21表面上的有机物与该现象有关。在本实施例中，在图3A的处理过程中，通过在氩气和氢气的混合气体等离子体中处理硅基板21的表面，使残留在硅基板表面上的有机物以炭化氢的形式而从硅基板表面除去，在图3B的处理开始时，在硅基板表面能够露出新鲜的硅表面。
图5表示的是这样形成的膜厚为10nm的氧化硅膜22的漏电流特性。其中，图5的测定是在12V的施加电压下进行的，与上述说明的以1V的施加电压测定时的漏电流相比，其数值有所不同。
参照图5，在图1所示的省略图3A的前处理过程的等离子体氧化膜中，可以获得与现有热氧化膜大致相同的漏电流密度，但是，在图3A的处理过程中，当进行由氩气进行的等离子体前处理时，漏电流值减少，特别是在图3(A)的处理过程中，在氩气和氢气的混合气体等离子体中进行前处理时进一步减少。
其中，在本实施例中，在图3B的处理过程中，通过氩气和氢气的混合气体等离子体而在硅基板21的表面形成氧化硅膜22，但是，通过使用氩气和氮气、或者氩气和氨气、或者氩气和氮气和氢气的混合气体等离子体，也可以形成氮化硅膜23。而且，通过使用氩气和氮气、氧气、或者氩气和氨、氧气、或者氩气和氮气、氢气、氧气的混合气体等离子体，也可以形成氮氧化硅膜24。
此外，在本实施方式中，也可以使用氦、氪、氙等其他稀有气体或者惰性气体来代替氩气。
此外，在本实施方式中，也可以使用NO、N2O、H2O等其他氧化气体或者氮化气体来代替氧气、氮气、氨气。
(第二实施方式)
图6A、6B表示是由本发明的第二实施方式进行的基板处理方法。
参照图6A，在硅基板21上形成有在前面的图3A、3B的处理或者其他处理过程中形成的氧化硅膜22，在图6A的处理过程中，通过氩气和氢气的混合气体等离子体以与图3A的处理同样的条件来处理上述氧化硅膜22的表面，除去残留在氧化硅膜22表面上的有机物。
然后，在图6B的处理过程中，以与图3B相同的条件使氩气和氧气的混合气体等离子体对这样处理的氧化硅膜22上进行作用，进一步使氧化膜成长而形成氧化膜25。
这样形成的氧化膜25具有与上述实施方式中说明的等离子体氧化膜同样优异的信赖性和漏电流密度。
其中，在图6B的处理过程中，通过使用氩气和氮气、或者氩气和氨、或者氩气和氮气、氢气的混合气体等离子体来氮化上述氧化硅膜22，也能够形成氮氧化硅膜26。
以上，使用图2A、2B的放射槽形天线15的微波等离子体基板处理装置对本实施例进行了说明，但是，在图2A的构造中，也可以这样构成，即，省略喷淋板14，直接从气体导入部14A将气体导入处理容器11中。此外，本发明并不局限于这种特定的基板处理装置，在平行平板型等离子体处理装置、ICP型等离子体处理装置、ECR型等离子体处理装置中也是有效的。
以上，对本发明的优选实施例进行了说明，但是，本发明并不限于这种特定的实施例，在记载于权利要求书的宗旨内，可以进行各种变形以及变更。

Claims (10)

1.一种基板处理方法，其特征在于，包括：
将硅基板表面暴露于惰性气体和氢气的混合气体等离子体中的第一处理过程；和
在所述第一处理过程之后，通过等离子体处理，对所述硅基板表面进行氧化处理、氮化处理以及氮氧化处理的任何一种处理的第二处理过程。
2.如权利要求1所述的基板处理方法，其特征在于：
所述惰性气体为稀有气体。
3.如权利要求1所述的基板处理方法，其特征在于：
所述惰性气体为氩气或者氪气或者氙气。
4.如权利要求1所述的基板处理方法，其特征在于：
所述第一处理过程和所述第二处理过程在同一等离子体处理装置中连续地进行。
5.如权利要求1所述的基板处理方法，其特征在于：
在所述第一处理过程中，所述惰性气体和氢气的混合气体等离子体通过微波而被激励。
6.如权利要求1所述的基板处理方法，其特征在于：
在所述第二处理过程中，所述等离子体处理是通过微波激励等离子体来进行的。
7.如权利要求1所述的基板处理方法，其特征在于：
所述等离子体通过从放射槽形天线放射的微波而被激励。
8.如权利要求1所述的基板处理方法，其特征在于：
在所述第一处理过程中，硅表面在所述硅基板的表面露出。
9.如权利要求1所述的基板处理方法，其特征在于：在所述第一处理过程中，在所述硅基板的表面形成有绝缘膜。
10.如权利要求9所述的基板处理方法，其特征在于：所述绝缘膜由氧化硅膜构成。
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