CN100418876C - 碳纳米管阵列制备装置及方法 - Google Patents
碳纳米管阵列制备装置及方法 Download PDFInfo
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Abstract
本发明涉及一种碳纳米管阵列制备装置,其包括:一反应腔;一局部加热装置,用以加热装载于该反应腔内的碳纳米管生长用催化剂;及一气态碳供给装置,用以在装载于该反应腔内的催化剂的上游位置向该反应腔提供一气态碳。本发明通过设置一局部加热装置及气态碳供给装置,可在反应腔的催化剂层位置处形成明显的温度梯度,及在反应腔内提供充足的碳源;其可实现碳纳米管阵列的快速生长,且可在基底上生长出单壁碳纳米管阵列。本发明还提供一碳纳米管阵列制备方法。
Description
【技术领域】
本发明涉及一种碳纳米管阵列制备装置及方法,尤其是利用化学气相沉积法的碳纳米管阵列制备装置及方法。
【背景技术】
碳纳米管是一种新型碳材料,由日本研究人员S Iijima于1991年发现,可参见″Helical microtubules of graphitic carbon″,S Iijima,Nature,vol.354,p56(1991)。碳纳米管具有极优异的导电特性,传热特性及机械特性等。目前已广泛应用于电子、光电,热传导等领域。
一般而言,碳纳米管分为单壁碳纳米管与多壁碳纳米管两种。多壁碳纳米管是由2~50层同心圆柱管状结构叠套而成,这些圆柱管由碳原子构成,就好像是把石墨片卷起来那样,碳原子在管壁上呈六边形排列,两端由五边形或七边形碳环组成的端冒封口,形成凹或凸的结构。单壁碳纳米管直径一般为1~6nm(最小直径为0.4nm),只有一层石墨结构。由于单壁碳纳米管具有单层壁结构,其相对于多壁碳纳米管而言,具有更少的原子缺陷。进而更具较大的应用潜力。
现有技术中,单壁碳纳米管的制备方法有:(1)Smalley等人在Science 273,483~487(1996),Crystalline Ropes of Metallic Carbon Nanotubes一文中揭露的激光蒸发法,其采用聚焦激光束消融碳-镍-钴混合物制备出由100~500根单壁碳纳米管组成的碳纳米管束,该碳纳米管的定向性较好,产出率为70%。(2)Journet等人在Nature 388,756~758(1997),Large-scale production ofsingle-walled carbon nanotubes by the electric-arc technique一文中揭露的电弧放电法,其采用直流电弧法制备出大量的单壁碳纳米管束,该大量单壁碳纳米管束的取向较混乱。(3)Dai等人在Chemical Physics Letters 292,567~574(1998),Chemical Vapor Deposition of Methane for Single-WalledCarbon Nanotubes一文中揭露的化学气相沉积法,其以甲烷为碳源气,氧化镍(NiO)、氧化钴(CoO)、或氧化镍/氧化钴(NiO/CoO)层作为催化剂;当采用晶态氧化铝纳米粒子作为催化剂支撑体时,制备出大量单根的单壁碳纳米管及少量的单壁碳纳米管束;当采用非晶态硅石(Amorphous Silica)作为催化剂支撑体时,仅能制备出单壁碳纳米管束。
综上所述,现有技术仅可制备出单根的单壁碳纳米管,及单根或定向性较好的单壁碳纳米管束;而难以实现单壁碳纳米管的阵列式生长,也即难以制备出单壁碳纳米管阵列。其将限制单壁碳纳米管阵列在场发射平面显示器、场发射平面光源、以及热界面材料等领域的应用。
有鉴于此,有必要提供一种碳纳米管阵列制备装置及方法,其可实现单壁碳纳米管阵列的生长。
【发明内容】
下面将以具体实施例说明一种碳纳米管阵列制备装置及方法,其可实现单壁碳纳米管阵列的生长。
为实现以上内容,提供一种碳纳米管阵列制备装置,其包括:
一反应腔;
一局部加热装置,用以加热装载于该反应腔内的碳纳米管生长用催化剂;及
一气态碳供给装置,用以在装载于该反应腔内的催化剂的上游位置向该反应腔提供气态碳。
优选的,所述局部加热装置为一高频炉或加热台。
优选的,所述气态碳供给装置包括一石墨块及一激光装置,通过该激光装置产生一激光束轰击该石墨块以产生气态碳。
可优选的,所述气态碳供给装置包括一对石墨电极及一电弧放电装置,通过电弧放电装置使该对石墨电极进行电弧放电以产生气态碳。
也可优选的,所述气态碳供给装置包括一石墨块及一与该石墨块串联形成电气回路的电源,通过该电源加热该石墨块至石墨气化温度以产生气态碳。
以及,提供一种碳纳米管阵列制备方法,其包括以下步骤:
将形成有一催化剂层的基底置于一反应腔内;
向该反应腔内通入保护气体,以使该反应腔内的空气排出;
对该反应腔内的基底进行局部加热,将催化剂加热至碳纳米管生长温度;
在基底的上游位置(Upstream)向反应腔内提供气态碳;
向该反应腔内通入碳源气,以进行碳纳米管阵列生长。
优选的,所述碳纳米管生长温度为650~1200℃。
优选的,所述气态碳是通过向一石墨块通以一加热电流使其到达高温而形成的。
可优选的,所述气态碳是通过采用激光束蒸发一石墨块而形成的。
也可优选的,所述气态碳是通过采用电弧放电法使一对石墨电极进行电弧放电而形成的。
所述基底包括硅、玻璃或氧化铝。
所述保护气体包括氩气、氮气、氦气、或其混合。
所述碳源气包括甲烷、乙烯或乙炔。
所述催化剂层的材质为铁、钴、镍、或其合金。
相对于现有技术,本技术方案所提供的碳纳米管阵列制备装置及方法,其通过一局部加热装置及气态碳供给装置,可在反应腔的催化剂层位置处形成明显的温度梯度,及在反应腔内提供充足的碳源;其可实现碳纳米管阵列的快速生长,且可在基底上生长出单壁碳纳米管阵列。
【附图说明】
图1是本发明第一实施例单壁碳纳米管阵列制备装置示意图。
图2是本发明第一实施例在950℃生长条件下生长出的单壁碳纳米管拉曼光谱(Raman Shift)图。
图3是本发明另一实施例在1000℃生长条件下生长出的单壁碳纳米管拉曼光谱(Raman Shift)图。
【具体实施方式】
下面结合附图将对本发明实施例作进一步的详细说明。
第一实施例
参见图1,本发明第一实施例所提供的碳纳米管阵列制备装置100,其包括一反应腔10,一局部加热装置20,及一气态碳供给装置30。
反应腔10具有一进气口12,及一与该进气口12相对设置的出气口14。该反应腔10可为现有技术中化学气相沉积法生长碳纳米管常用的石英管。该进气口12与出气口14分别设于该反应腔10的两端。进气口12可用于向反应腔10提供保护气体(如,氩气、氮气、氦气、或其混合)及生长碳纳米管用碳源气(如,甲烷、乙烯或乙炔等碳氢化合物)。出气口14可用于排放气体。
局部加热装置20用以对装载于反应腔10内的基底40进行局部加热,以将基底40表面上的催化剂层42加热至碳纳米管生长温度。该催化剂层42用作碳纳米管生长的触媒层。该局部加热装置20对应催化剂42设置,该局部加热装置20的选用以能实现仅对形成在基底40表面的催化剂42加热为佳。本实施例中选用高频炉,该高频炉位于反应腔10外部,其只能对导体加热;因此其可实现仅对形成在基底40表面的催化剂层42加热,进而可在催化剂层42位置与催化剂层42上方形成明显的温度梯度,有利于碳纳米管的快速生长。当然,局部加热装置20也可选用一加热台,其可对整个基底40加热,但非对整个反应腔加热;其也可在催化剂层42位置与催化剂层42上方形成明显的温度梯度。
气态碳供给装置30用以向反应腔10提供一额外碳源。该气态碳供给装置30可产生气态碳,并在反应腔10的装载有碳纳米管生长用催化剂层42的上游位置提供气态碳。所述上游位置是指催化剂层42的位于进气口12一侧某一位置处。所述气态碳供给装置30与反应腔10密封连接。本实施例中,该气态碳供给装置30位于反应腔10的外部,其包括一石墨块(图未示)及一激光装置(图未示),该激光装置产生一激光束轰击该石墨块即可产生一气态碳,该气态碳可经由通入惰性气体将其导入反应腔10内的催化剂层42的上游位置。该气态碳供给装置30也可采用其它结构形式,如:其包括一对石墨电极及一电弧放电装置,将该对石墨电极装载于该电弧放电装置内以进行电弧放电;进而产生一气态碳。向该电弧放电装置内通入一惰性气体可将该气态碳导入反应腔10内的催化剂层42的上游位置。
当然,也可以另一种气态碳供给装置,其包括一石墨块及与该石墨块串联形成一电气回路的电源。该石墨块直接放置于反应腔内装载催化剂的上游位置,该电源设于反应腔10外部;使用一穿过进气口12的导线实现石墨块与电源的电气连接。该电源可于石墨块两端施加加热电路以使石墨块到达石墨的气化温度而于反应腔10装载催化剂层42的上游位置产生一气态碳。
下面将详细描述本实施例中碳纳米管阵列制备装置100的操作过程。
(1)向反应腔10提供一上表面有一催化剂层42的基底40。该基底40的基体材质可为半导体材料(如,硅)、或玻璃及氧化铝等。所述催化剂层42为一金属膜,其厚度以纳米量级(小于1μm)为佳;该催化剂层42的材质可选用常用的碳纳米管生长用催化剂,如铁、钴、镍、或其合金等。
(2)经由该进气口12向该反应腔10内通入保护气体,以使该反应腔10内的空气经由该出气口14排除。并且,在后续催化剂层42加热及碳纳米管生长过程中持续通入该保护气体。其中,保护气体可选用氩气、氮气、氦气等惰性气体,或其混合。
(3)通过一局部加热装置30,将该基底40表面的催化剂层42加热至碳纳米管生长温度。碳纳米管生长温度一般为650℃~1200℃。本实施例中,局部加热装置30为一高频炉,其将基底50加热至950℃。
(4)在基底50的上游位置(Upstream)向反应腔提供一气态碳。该气态碳是由气态碳供给装置30提供,该气态碳的提供方法可为下列方法之一:(1)启动Nd:YAG等激光装置产生一激光束轰击一石墨块产生一气态碳,同时采用一惰性气体将该气态碳导入反应腔10中的基底50的上游位置。通过控制激光功率可控制气态碳的蒸出量,进而可控制碳纳米管的生长速度。(2)将一对石墨电极装载于电弧放电装置,并使该对石墨电极的间距足够小(小于1mm);启动该电弧放电装置使石墨电极发生电弧放电产生一气态碳。向电弧放电装置内通入一惰性气体以将该气态碳导入反应腔10中的基底50的上游位置。通过控制电弧放电的放电电流的大小可控制气态碳的蒸出量,进而可控制碳纳米管的生长速度。(3)在反应腔内装载的催化剂层42的上游位置放置一石墨块,通过一位于反应腔10外部的电源向石墨块通入加热电流,使其到达石墨气化温度以在催化剂层42的上游位置产生一气态碳。通过控制加热电流的大小可控制气态碳的蒸出量,进而可控制碳纳米管的生长速度。
(5)经由进气口12向该反应腔10内通入一碳源气,以进行碳纳米管生长。为精确控制碳纳米管阵列的生长高度,以在在通入气态碳的同时通入碳源气为佳。在碳源气及保护气体的携带作用下,气态碳被携带至基底40上的催化剂层42位置。碳源气在催化剂层42的高温下分解出碳和氢气;碳源气遇高温分解出的碳及向反应腔10通入的气态碳与催化剂层42中的催化剂粒子形成金属碳化物,当金属碳化物中的碳达到饱和后,其中的碳将向低温方向(即催化剂层42上方位置)析出而形成碳纳米管。其中,碳源气可选用碳纳米管生长常用的甲烷、乙烯或乙炔等碳氢化合物。图1中箭头所指方向为气流方向。在碳纳米管生长过程中,保护气体与碳源气的体积比优选为1∶1~1∶10;反应腔10内的气压优选为400Torr~600Torr;保护气体的流速优选为200sccm~500sccm;碳源气的流速优选为20sccm~60sccm。本实施例中,反应腔10内的气压为500Torr;保护气体的流速为360sccm;碳源气选用乙炔,其流速为40sccm。
本实施例中,单壁碳纳米管的生长速率极快,在40秒生长时间中单壁碳纳米管阵列高度达1mm以上,甚至可达2.5mm/s(毫米每分钟)。图2为本实施例中,950℃生长条件下生长出的单壁碳纳米管阵列中的单壁碳纳米管的拉曼光谱图;由图2可知,该单壁碳纳米管阵列中单壁碳纳米管的最高计数径向呼吸模式显示179.92cm-1,其对应的单壁碳纳米管的直径为1.29nm。
本实施例中,通过实现基底40的局部加热,在反应腔10的基底40位置处形成明显的温度梯度,其有利于碳向温度低方向析出及催化剂的成核率的提升,进而实现碳纳米管的快速生长;通过提供气态碳,有其利于碳纳米管快速生长过程中的碳供给;并且,充足的碳分子与催化剂形成金属碳化物可放出大量热。而单壁碳纳米管的热传导性质最佳,为使热量快速传导出去,其将可在基底40上生长出单壁碳纳米管阵列。
另一实施例中,设置碳纳米管生长温度为1000℃。图3为1000℃生长条件下生长出的单壁碳纳米管阵列中的单壁碳纳米管的拉曼光谱图;由图3可知,该单壁碳纳米管阵列中单壁碳纳米管的径向呼吸模式显示的主要峰位有184.9cm-1,165.76cm-1,148.21cm-1;其分别对应的单壁碳纳米管的直径为1.25nm,1.40nm,1.58nm。
另外,本领域技术人员还可在本发明精神内做其它变化,如适当变更反应腔内的气压,保护气体及碳源气的流速,碳纳米管阵列生长温度等设计以用于本发明,只要其不偏离本发明的技术效果均可。这些依据本发明精神所做的变化,都应包含在本发明所要求保护的范围之内。
Claims (16)
1. 一种碳纳米管阵列制备装置,其包括:
一反应腔,该反应腔内设置有用以生长碳纳米管的催化剂;
一局部加热装置,该局部加热装置对应催化剂设置,用以加热催化剂;及
一气态碳供给装置,该气态供给装置与反应腔密封连接,用以向该反应腔内催化剂的上游位置提供气态碳。
2. 如权利要求1所述的碳纳米管阵列制备装置,其特征在于所述局部加热装置为一高频炉或加热台。
3. 如权利要求1所述的碳纳米管阵列的制备装置,其特征在于,所述局部加热装置位于反应腔外部,催化剂的下方。
4. 如权利要求1所述的碳纳米管阵列制备装置,其特征在于所述气态碳供给装置包括一石墨块及一激光装置,通过该激光装置产生一激光束轰击该石墨块以产生气态碳。
5. 如权利要求1所述的碳纳米管阵列制备装置,其特征在于所述气态碳供给装置包括一对石墨电极及一电弧放电装置,通过电弧放电装置使该对石墨电极进行电弧放电以产生气态碳。
6. 如权利要求1所述的碳纳米管阵列制备装置,其特征在于所述气态碳供给装置包括一石墨块及一与该石墨块串联形成电气回路的电源,通过该电源加热该石墨块至石墨气化温度以产生气态碳。
7. 如权利要求1所述的碳纳米管阵列的制备装置,其特征在于,所述的气态碳供给装置位于反应腔外部。
8. 一种碳纳米管阵列制备方法,其包括以下步骤:
(1)将形成有一催化剂层的基底置于一反应腔内;
(2)向该反应腔内通入一保护气体;
(3)对该基底进行局部加热,将催化剂加热至碳纳米管生长温度;
(4)在该基底的上游位置向反应腔内提供气态碳;
(5)向该反应腔内通入碳源气,以进行碳纳米管阵列生长。
9. 如权利要求8所述的碳纳米管阵列制备方法,其特征在于所述碳纳米管生长温度为650~1200℃。
10. 如权利要求8所述的碳纳米管阵列制备方法,其特征在于所述气态碳是通过向一石墨块通以一加热电流使其到达高温而形成的。
11. 如权利要求8所述的碳纳米管阵列制备方法,其特征在于所述气态碳是通过采用激光束蒸发一石墨块而形成的。
12. 如权利要求8所述的碳纳米管阵列制备方法,其特征在于所述气态碳是通过采用电弧放电法使一对石墨电极进行电弧放电而形成的。
13. 如权利要求8所述的碳纳米管阵列制备方法,其特征在于所述基底包括硅、玻璃或氧化铝。
14. 如权利要求8所述的碳纳米管阵列制备方法,其特征在于所述保护气体包括氩气、氮气、氦气、或其混合。
15. 如权利要求8所述的碳纳米管阵列制备方法,其特征在于所述碳源气包括甲烷、乙烯或乙炔。
16. 如权利要求8所述的碳纳米管阵列制备方法,其特征在于所述催化剂层的材质为铁、钴、镍、或其合金。
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JP4436821B2 (ja) | 2010-03-24 |
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US8142568B2 (en) | 2012-03-27 |
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US20090269257A1 (en) | 2009-10-29 |
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