CN1270920A - 碳毫微管的形成方法 - Google Patents

碳毫微管的形成方法 Download PDF

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CN1270920A
CN1270920A CN00106211A CN00106211A CN1270920A CN 1270920 A CN1270920 A CN 1270920A CN 00106211 A CN00106211 A CN 00106211A CN 00106211 A CN00106211 A CN 00106211A CN 1270920 A CN1270920 A CN 1270920A
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张震
郑皙在
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Jim Xicui company
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Abstract

本发明涉及一种容易通过高密度等离子体形成经纯制的碳毫微管的方法,由该碳毫微管中已除去石墨相或碳颗粒。以1011cm－3或更高的等离子体密度使用等离子体化学气相沉积法在基底上生长碳毫微管层。碳毫微管的形成方法包括:通过等离子体沉积在基底上生长碳毫微管层直至预定的厚度;通过等离子体蚀刻纯制碳毫微管;以及重复碳毫微管的生长和纯制。在等离子体蚀刻时,使用包含卤素的气体作为源气体,例如四氟化碳气体。

Description

碳毫微管的形成方法
本发明涉及碳毫微管的形成方法，更具体而言是涉及使用等离子体来生长和纯制碳毫微管。
碳是包括人在内的所有生物的最重要的组成元素，其与氧、氢、氮等结合，而且具有独特的晶体结构，包括钻石、石墨、富勒烯和碳毫微管。具体而言，碳毫微管是指生长有单壁或多个壁的螺旋管状结构，其可通过卷绕由多个六方体形成的片材而形成的，而所述片材是通过各碳原子结合三个相邻碳原子形成的。碳毫微管的直径在几毫微米至几百毫微米之间的数量级上。根据螺旋管的卷绕形状和直径，碳毫微管有类似于金属作为导体或者作为半导体的功能。同样，其具有预定长度的中空结构使得产生良好的机械、电和化学性质，因此碳毫微管可作为场发射装置、氢容器和可充电电池的电极。
最开始是Sumio Iijima在题目为“石墨碳的螺旋微管(HelicalMicrotubules of Graphitic Carbon)，，的文章中(Nature，第354卷，1991年11月7日，第56-58页)发现并报道了在两个石墨棒之间通过电弧放电产生的碳毫微管。该技术通常用于制造碳毫微管，但是相对于最终产物，纯碳毫微管的产率仅为约15％。因此，对于特殊的装置应用必须进行复杂的纯制过程。
其他常规制造碳毫微管的方法描述于Michiko Kusunoki的题目为“通过升华分解碳化硅而自组的外延碳毫微管膜(Epitaxial Carbon NaotubeFilm Self-organized by Sublimation Decomposition of Silicon Carbide)”的文章中(Appl.Phys.Lett.，第71卷，2620页，1977年)，其是在高温下通过用激光照射石墨或碳化硅来制造碳毫微管。在该情况下，碳毫微管是在约1200℃或更高的温度下由石墨以及在约1600-1700℃下由碳化硅制成的。但是，该方法也需要多个纯制步骤，并增加成本。另外，该方法在大装置应用时有困难。
W.Z.Li等人在题目为“直线排列的碳毫微管的大规模合成(Large-Scale Synthesis of Aligned Carbon Nanotubes)”的文章中(Science，第274卷，1996年12月6日，1701-1703页)报道了通过热分解烃系列气体由化学气相沉积(CVD)制造碳毫微管的方法。该技术仅适用于不稳定的气体，如乙炔或苯。例如，该技术不能使用甲烷(CH4)来制造碳毫微管。
本发明的目的是提供一种形成碳毫微管的方法，其中使用高密度等离子体生长高密度的碳毫微管。
本发明的另一个目的是提供一种形成碳毫微管的方法，其中碳毫微管是通过使用高密度等离子体除去石墨或碳颗粒来纯制碳毫微管，使得碳毫微管可容易地高密度生长。
为达到本发明的第一个目的，提供一种形成碳毫微管的方法，其中以1011cm-3或更高的密度使用等离子体化学气相沉积法在基底上生长碳毫微管。优选的是，基底是其上形成有催化金属层的无定形硅或聚硅基底。在碳毫微管层的生长过程中，可使用烃系列气体作为等离子体源气体，基底的温度可在600-900℃范围内，而压力可在10-1000mTorr范围内。
为达到本发明的第二个目的，提供一种形成碳毫微管的方法，其包括通过等离子体沉积在基底上生长碳毫微管层，直至具有预定的厚度。接下来，通过等离子体蚀刻纯制碳毫微管。然后重复碳毫微管的生长和纯制。
优选的是，生长碳毫微管层是在1011cm-3或更高的高等离子体密度下通过等离子体化学气相沉积法来进行的。在纯制碳毫微管层的过程中，可使用含卤素气体或含氧气体作为用于蚀刻的等离子体源气体。
根据本发明，通过用高密度等离子体分解稳定的CH4气体可生长高密度的碳毫微管。同样，可通过重复碳毫微管的生长和纯制过程容易地形成高纯度的碳毫微管。
参考附图更详细地说明优选的实施方案，本发明的以上目的和优点由此将更为明显，在附图中：
图1是显示用于形成根据本发明之优选实施方案的碳毫微管的基底的截面图；
图2-6是说明形成根据本发明之优选实施方案的碳毫微管的各个阶段的截面图；
图7是在本发明的优选实施方案中形成的碳毫微管平面的扫描电子显微(SEM)图象；
图8是在本发明的优选实施方案中形成的碳毫微管的垂直截面的SEM图象；
图9是在本发明的优选实施方案中形成的碳毫微管的透射电子显微(TEM)图象；
图10是在本发明的优选实施方案中形成的碳毫微管经放大的TEM图象；以及
图11是比较在本发明的优选实施方案中形成的碳毫微管与常规方法形成的碳毫微管的场发射性质的图。
以下将参考附图更为完全地描述本发明，其中显示了本发明的优选实施方案。但是，本发明还可有许多不同的形式，而且并不仅限于在此所述的实施方案。这些实施方案的提供完全是为了使公开更充分，并使本领域技术人员更好地理解本发明的概念。
参考图1，其示出了用于形成根据本发明之优选实施方案的碳毫微管的基底。在预定的基底11上顺序地形成硅薄膜12和催化金属层13。基底11是刚性绝缘基底，其能够耐受随后的等离子体处理。在本实施方案中，使用玻璃基底，其使得在其上容易地沉积硅薄膜12。硅薄膜12是由无定形硅或聚硅形成的。催化金属层13可由过渡金属如镍、钴和铁以及它们的合金形成。
在本实施方案中，在基底11上沉积无定形硅至几百—几千埃的厚度，然后在其上沉积镍至几十—几百埃的厚度。当由无定形硅形成硅薄膜12并随后在600℃或更高的温度下进行如图2所示的等离子体沉积处理时，其上沉积的镍扩散进无定形硅薄膜12中，这产生了如图2所示的金属诱导结晶化的聚硅薄膜14。金属扩散进无定形硅薄膜中有助于无定形硅薄膜的结晶，而且在碳毫微管形成过程中无需其他步骤。同样，在聚硅薄膜的表面上存在相当量的镍，其在金属诱导结晶化中始终存在，并在随后的过程中对于生长碳毫微管起到催化金属的作用。
然后在催化金属层13上生长碳毫微管层。图2-6是说明形成根据本发明之优选实施方案的碳毫微管的各个阶段的截面图。
首先参考图2，将具有催化金属层13的基底11放置在等离子体化学气相沉积装置中，以生长碳毫微管层15。在本实施方案中，使用能够通过施用放射频率(RF)功率来产生高密度等离子体的电感耦合等离子体装置(ICP)。用于生长碳毫微管层15的沉积等离子体源气体18可以是包括碳原子的烃系列气体，如乙炔或苯。在本实施方案中，使用甲烷(CH4)，而且流速为10sccm。此时，以10sccm的流速一起供应氦(He)。对于生长碳毫微管层15，RF功率保持在1kW，基底11的温度保持在600-900℃，而装置的内压力保持在10-1000mTorrr。为促进碳毫微管层15的生长反应，可添加氮(N2)气体或氢(H2)气体。
在本实施方案中，沉积等离子体18保持在1011cm-3的高密度下，而碳毫微管层15生长至范围是3-300nm的希望厚度。碳毫微管层15的厚度随沉积时间的增加而增加，而沉积时间可在几秒—几百秒的范围内变化。在等离子体沉积模式中，也可在生长碳毫微管层15的过程中在碳毫微管的端部或侧壁上形成石墨相或无定形碳颗粒，使得纯碳毫微管的密度非常低。
如前所述，在基底11上形成有无定形硅薄膜12和催化金属层13时，催化金属在生长碳毫微管层15的过程中扩散进无定形硅层12中，产生金属诱导结晶化的聚硅层14，在该层上保留预定量的催化金属。
然后参考图3，在改变等离子体化学气相装置的条件后，即、从等离子体沉积模式转变为等离子体蚀刻模式后，在生长碳毫微管层15的过程中形成的石墨相或无定形碳颗粒被蚀刻掉，以纯制碳毫微管层15，并产生经纯制的碳毫微管层17(1)。在转变为等离子体蚀刻模式的模式转换之前，用氮气或惰性气体彻底清洗等离子体化学气相沉积装置。等离子体蚀刻的处理条件设定成基本上与图2所示的等离子体沉积模式相同，但等离子体源气体的种类不同。
用于等离子体蚀刻模式的等离子体源气体可以是包含卤素元素如F、Cl或Br的气体或者含氧的气体。在本实施方案中，使用含氟的气体，例如四氟化碳(CF4)。通过与碳离子反应，由四氟化碳气体分离出来的氟离子产生高度挥发性的氟化碳系列气体(CFn)。离子化的氟易于与从石墨相或无定形碳颗粒中分解的碳离子反应，因为与碳毫微管层15相比，所述碳颗粒的结合力更低，使得石墨相或无定形碳颗粒能够被高蚀刻选择性地由碳毫微管中除去。
现参考图4，图3中所示的等离子体蚀刻模式转变为等离子体沉积模式。在此，清洗等离子体化学气相沉积装置，以便完全从该装置中除去氟离子。等离子体沉积模式在与图3所示相同的条件下进行等离子体沉积模式，这在经纯制的碳毫微管层17(1)上产生另一个碳毫微管层15。
参考图5，图4的等离子体沉积模式转变为等离子体蚀刻模式。在此，彻底清洗等离子体化学气相沉积装置。在与图3所示相同的条件下进行等离子体蚀刻模式，产生另一个经纯制的碳毫微管层17(2)。
参考图6，重复n次以上所述的等离子体沉积模式和等离子体蚀刻模式。根据最终碳毫微管层的厚度来适当地确定重复次数。
图7是在本发明之优选实施方案中形成的碳毫微管平面的扫描电子显微(SEM)图象。图8是在本发明之优选实施方案中形成的碳毫微管在不同放大倍数时的垂直截面的SEM图象。如图8所示，碳毫微管很好地在基底上排成一行。
图9是在本发明之优选实施方案中形成的碳毫微管的透射电子显微(TEM)图象。在图9中示出了高度缠绕的丝。图10是在本发明之优选实施方案中形成的碳毫微管经放大的TEM图象。在图10中，单壁碳毫微管非常高密度地缠绕成束。
图11是比较在本发明的优选实施方案中形成的碳毫微管与常规方法形成的碳毫微管的场发射性质的图。常规方法是指连续生长碳毫微管层的技术，与本发明不同，其没有交替地使用等离子体沉积模式和等离子体蚀刻模式。测定单位面积为1cm2的场发射电极的场发射性质。从图11中可以得出以下结论：通过从碳毫微管的尖部或侧壁上除去石墨相或无定形碳颗粒来纯制碳毫微管能够在低电场下得到高电流发射。
根据本发明形成碳毫微管的方法可容易地在高密度等离子体条件下生长高密度的碳毫微管，其使用例如甲烷气体作为源气体。另外，在生长碳毫微管的过程中形成的石墨相或无定形碳颗粒可容易地通过重复等离子体沉积模式和等离子体蚀刻模式来除去，其产生具有良好场发射性质的碳毫微管。
虽然已参考优选实施方案具体地表示和描述了本发明，但本领域技术人员应理解的是，在不偏离本发明的实质和范围的情况下还可对其形式和细节进行各种的改变，而本发明的范围应由所附的权利要求书来限定。

Claims (13)

1、一种形成碳毫微管的方法，其中，以1011cm-3或更高的等离子体密度使用等离子体化学气相沉积法在基底上生长碳毫微管层。
2、如权利要求1所述的方法，其中，所述基底是其上形成有催化金属层的无定形硅或聚硅基底。
3、如权利要求1所述的方法，其中，在碳毫微管层的生长过程中，使用烃系列气体作为等离子体源气体，基底的温度在600-900℃范围内，而压力在10-1000mTorr范围内。
4、一种形成碳毫微管的方法，其包括以下步骤：
通过等离子体沉积在基底上生长碳毫微管层，直至具有预定的厚度；
通过等离子体蚀刻纯制碳毫微管；以及
重复碳毫微管的生长和纯制。
5、如权利要求4所述的方法，其中，生长碳毫微管层是在1011cm-3或更高的高等离子体密度下通过等离子体化学气相沉积法来进行的。
6、如权利要求4所述的方法，其中，所述基底是其上形成有催化金属层的无定形硅或聚硅基底。
7、如权利要求4所述的方法，其中，在碳毫微管层的生长过程中，使用烃系列气体作为等离子体源气体，基底的温度在600-900℃范围内，而压力在10-1000mTorr范围内。
8、如权利要求4所述的方法，其中，在纯制碳毫微管层的过程中，使用含卤素的气体作为用于蚀刻的等离子体源气体。
9、如权利要求8所述的方法，其中，在纯制碳毫微管层的过程中，使用含氟的气体作为用于蚀刻的等离子体源气体。
10、如权利要求9所述的方法，其中，在纯制碳毫微管层的过程中，使用四氟化碳(CF4)气体作为用于蚀刻的等离子体源气体。
11、如权利要求4所述的方法，其中，在纯制碳毫微管层的过程中，使用含氧的气体作为用于蚀刻的等离子体源气体。
12、如权利要求4所述的方法，其中，在生长碳毫微管的过程中，碳毫微管层的厚度一次生长至厚度为3-300nm。
13、如权利要求6所述的方法，其中，所述碳毫微管层生长在金属诱导结晶化的聚硅层上，该聚硅层是通过沉积在无定形硅基底上的催化金属的扩散而由无定形硅基底转变的。
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