CN1239387C - 碳纳米管阵列及其生长方法 - Google Patents
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Abstract
本发明提供一种在金属基底上生长碳纳米管阵列的方法,其包括以下步骤:提供一金属基底;在金属基底表面上沉积一层硅过渡层;将催化剂沉积于该硅层表面;通入碳源气反应,长出碳纳米管阵列。通过本发明的方法可实现在金属基底上生长碳纳米管阵列,而且对金属基底材料基本无选择性。本发明还提供一种生长在金属基底上的碳纳米管阵列。
Description
【技术领域】
本发明涉及一种碳纳米管阵列及其生长方法,尤其涉及一种在金属基底上生长的碳纳米管阵列及其生长方法。
【背景技术】
碳纳米管是在1991年由Iijima在电弧放电的产物中首次发现的中空碳管,发表在1991年出版的Nature354,56,HelicalMicrotubules of Graphitic Carbon。碳纳米管具有优良的综合力学性能,如高弹性模量、高杨氏模量和低密度,以及优异的电学性能、热学性能和吸附性能。随着碳纳米管螺旋方式的变化,碳纳米管可呈现出金属性或半导体性质。由于碳纳米管的优异特性,因此可望其在纳米电子学、材料科学、生物学、化学等领域中发挥重要作用,而碳纳米管阵列因其中的碳纳米管排列整齐有序,使其更有利于工业应用。
目前形成有序碳纳米管阵列的方法主要是化学气相沉积法(CVD)。化学气相沉积主要是运用纳米尺度的过渡金属或其氧化物作为催化剂,在相对低的温度下热解含碳的源气体来制备碳纳米管阵列。
当碳纳米管阵列应用于场发射显示器、电子枪、大功率行波管等器件时,因为场发射平面显示点阵的寻址要求具有良好导电性,并且能够承载较大电流的电极;电子枪、大功率行波管等器件的阴极也需要能承载大电流的基底,对于这些应用,金属基底仍然为最佳材料。
而目前碳纳米管阵列的生长多以硅、二氧化硅、玻璃等为基底,而较少用金属为基底,这主要是因为通常金属材料会强烈影响化学气相沉积的生长环境,或者因为金属易于与催化剂形成合金,从而使催化剂失去活性,或者因为金属自身具有催化作用而强烈分解碳源气形成积碳,导致无法正常生长碳纳米管。
申请人为北京大学的一份公开日为2000年1月19日,公开号为CN1241813A的中国专利申请公开了一种碳纳米管的组装结构及一种碳纳米管的组装方法。该组装结构包括金属基底和碳纳米管两部分,该碳纳米管竖立于基底表面。该组装方法是先将生长出的单壁碳纳米管分离,纯化后制成水溶胶体;长时间存放后,按水溶液不同的柱高位置,分选所需长度的碳纳米管原液;然后按所需的原液加入去离子水稀释,用甩胶法或浸入法将碳纳米管组装在洁净的金属基底表面。
但是,该组装方法并未能实现在金属基底上制备碳纳米管阵列,且该法需将生长的碳纳米管纯化、分离、制成水溶胶,还需保存一个月左右,耗时太长,不利于实际生产应用。
Ch.Emmenegger等人在文献Applied Surface Science 162-163452-456(2000),Carbon nanotube synthetisized on metallic substrate中揭示了一种在铝基底上形成碳纳米管阵列的方法。他们通过在铝基底上涂敷上Fe(NO3)3,通过热处理使Fe(NO3)3涂层形成纳米级Fe2O3颗粒,然后通入乙炔碳源气与保护气体的混合气体使碳纳米管阵列长出。
但是,在形成碳纳米管阵列过程中为避免金属基底影响化学气相沉积的生长环境,或者与催化剂形成合金,或者因其自身具有催化作用而强烈分解碳源气形成积碳,该法对金属基底材料具有很大的选择性,可以生长的金属材料只能限制在铝、镍等几种材料,从而限制其作为纳米器件更为广阔的应用。
【发明内容】
本发明要解决的技术问题是克服以上不足,提供一种对金属基底材料无选择性,使碳纳米管阵列生长在金属基底上的方法。
本发明另一目的是提供一种适于实用的生长在金属基底上的碳纳米管阵列。
本发明解决技术问题的技术方案是:提供一金属基底,在金属基底表面上沉积一层硅过渡层,将催化剂沉积于该硅过渡层表面,通入碳源气,使碳纳米管阵列长出。
本发明的另一目的是这样实现的:提供一种碳纳米管阵列,其包括一金属基底及形成于基底上的碳纳米管阵列,该金属基底和碳纳米管阵列之间还有一沉积于金属基底上的硅层。
与现有技术相比较,本发明通过在金属基底表面形成一层硅过渡层,然后在硅过渡层上沉积催化剂,从而避免金属基底与催化剂的直接接触,避免了金属基底对碳纳米管生长环境的影响,也避免了基底与催化剂形成合金,或者因其自身具有催化作用而强烈分解碳源气形成积碳,其碳纳米管阵列的生长条件与在硅基底上生长条件相同,因此实现了在金属基底上生长碳纳米管阵列,且原则上可以在任何一种微电子工艺适用的金属材料上生长,而且生长形态不受影响,在生产工艺中有实际意义。
与现有技术相比较,本发明通过在金属基底表面形成一层硅过渡层,然后在硅过渡层上沉积催化剂来生长的碳纳米管阵列,因其基底为金属,从而导电性能更好,能承载较大电流,更适于作为场发射显示器、电子枪、大功率行波管等器件的电极;而且该碳纳米管阵列的金属基底可根据其应用需要而选择不同的金属基底,使其在纳米器件上应用更为广泛。
【附图说明】
图1是本发明在金属基底上生长碳纳米管阵列的方法流程图。
图2是金属基底的示意图。
图3是沉积有硅过渡层的金属基底示意图。
图4是图3所示的硅过渡层上沉积有催化剂的金属基底示意图。
图5是将图4所示的金属基底热处理后的示意图。
图6是本发明碳纳米管阵列示意图。
图7是在硅片上用磁控溅射法形成的钽(Ta)电极图形的扫描电镜照片(SEM,Scanning Electron Microscope)。
图8是以本发明的方法在图7所示的Ta电极图形上生长所得的碳纳米管阵列的SEM照片。
图9是以本发明的方法在电子枪的镍(Ni)阴极帽上生长所得的碳纳米管阵列的SEM照片。
【具体实施方式】
如图1所示,在金属基底上生长碳纳米管阵列的方法包括以下步骤:
步骤1是提供一金属基底,该金属基底可用金属板或在所需基片上形成的金属电极;
步骤2是在金属基底上沉积一层硅,该硅层厚度为几十纳米;
步骤3是在步骤2形成的硅层上形成金属催化剂层,厚度为几个纳米;
步骤4是将步骤3所形成的基底进行热处理;
步骤5是通入碳源气与保护气体的混合气体,长出碳纳米管阵列。
下面将结合图示具体描述在金属基底上生长碳纳米管阵列的方法。
请参阅图2,首先提供一金属基底11,可直接选用金属板或者在所需基片上形成的金属电极。其中,基片可选用硅片、石英片、玻璃等材料,但要求具有一定的平整度,然后可通过电镀、磁控溅射等方法在基片上形成金属电极。将选用的金属板或形成的金属电极通过机械抛光、电化学抛光等手段使其表面具有一定的平整度。
原则上,对于金属板材料和金属电极材料的选择没有特殊的要求,任何一种微电子工艺适用的金属材料皆可用于生长碳纳米管阵列,但需要注意是:金属板材料或金属电极材料在化学气相沉积的生长温度下满足以下4个条件:
1.不发生熔化;
2.不与所用基片发生共熔;
3.从室温到CVD生长温度的温度范围内,其热膨胀系数与所用基片相容;
4.不会因吸氢而产生膨胀或碎裂等变化。
本实施例中选用镍(Ni)或不锈钢等为金属板材料,选用钽(Ta)、Ni或银(Ag)等为金属电极材料。
利用热蒸发或电子束蒸发的方法在上述金属基底11表面蒸镀一层硅过渡层21,其厚度为几十纳米。请参阅图4,然后将金属催化剂31利用电子束蒸发沉积、热沉积或溅射法等方法形成在硅过渡层21上,其厚度为几纳米到几十纳米不等,其中,金属催化剂31可为铁(Fe)、钴(Co)、镍(Ni)或其合金之一,本实施例中选用铁为催化剂,沉积厚度为5纳米。
将沉积有催化剂31的基底11在空气中,在300-400℃热处理约10小时,使催化剂31氧化收缩成颗粒32,如图5所示。
请参阅图6,将上述热处理后的基底11装入一反应舟中,一般为石英反应舟,将反应舟装入管状石英炉中央的反应室里,在气体保护下加热至一预定温度,其中,该保护气体为惰性气体或氮气,本实施例选用氩气,该预定温度因催化剂不同而不同,因本实施例选用铁为催化剂,则一般加热到500-700℃,优选为650℃。
通入氢气或氨气还原使催化剂颗粒32形成纳米级的催化剂颗粒(图未示)(此步骤根据情况亦可省略)。通入碳源气与保护气体的混合气体,其中碳源气为碳氢化合物,可为乙炔、乙烯等,本实施例选用乙炔为碳源气;该保护气体为惰性气体或氮气,本实施例选用氩气,反应5-30分钟长出碳纳米管阵列51。
该碳纳米管阵列51中的碳纳米管排列整齐有序,且生长方向基本垂直于金属基底,适于作为场发射显示器,电子枪等大功率电子器件的阴极。
当然也可使反应室为真空状态,只通入碳源气反应,如乙炔,长出碳纳米管阵列51。
请一并参阅图7至图9,图7是在硅基片上用磁控溅射方法形成的Ta电极图形的SEM照片,图8是以本发明所述方法在图7所示的Ta电极图形上生长所得的碳纳米管阵列的SEM照片。图9是用本发明所述方法在电子枪的Ni阴极帽上生长所得的碳纳米管阵列的SEM照片。从图中可看出,以本发明的方法在不同的金属基底上所形成的碳纳米管中的碳纳米管都排列整齐有序,且基本垂直于金属基底。
Claims (13)
1.一种碳纳米管阵列,其包括一金属基底及形成于基底上的碳纳米管阵列,其特征在于该金属基底和碳纳米管阵列之间还有一沉积于金属基底上的硅层。
2.如权利要求1所述的碳纳米管阵列,其特征在于该硅层厚度为几十纳米。
3.如权利要求2所述的碳纳米管阵列,其特征在于在金属基底为钽、镍、银或不锈钢之一。
4.一种如权利要求1所述的碳纳米管阵列的生长方法,其特征在于包括以下步骤:
(1)提供一金属基底;
(2)在金属基底表面上沉积一层硅过渡层;
(3)将催化剂沉积于该硅层表面;
(4)通入碳源气反应,长出碳纳米管阵列。
5.如权利要求4所述的生长方法,其特征在于步骤(1)中的金属基底为金属板或为在基片上形成的金属电极。
6.如权利要求5所述的生长方法,其特征在于该金属板材料为镍或不锈钢,该金属电极材料为钽、镍或银之一。
7.如权利要求4所述的生长方法,其特征在于步骤(2)中在金属基底表面沉积硅过渡层之前还包括将金属基底抛光至具有一定平整度。
8.如权利要求4所述的生长方法,其特征在于步骤(3)中所用催化剂为铁、钴、镍或其合金之一。
9.如权利要求4所述的生长方法,其特征在于步骤(4)通入碳源气反应前将沉积有催化剂的基底在空气中于300-400℃热处理10小时。
10.如权利要求9所述的生长方法,其特征在于热处理后,通入碳源气反应之前还包括将基底在保护气体中预加热到500-700℃。
11.如权利要求10所述的生长方法,其特征在于保护气体为氮气或惰性气体。
12.如权利要求10所述的生长方法,其特征在于预加热后,通入碳源气之前还包括将催化剂还原成纳米级颗粒。
13.如权利要求4所述的生长方法,其特征在于步骤(4)中,通入的碳源气为乙炔或乙烯。
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US7288321B2 (en) | 2007-10-30 |
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