CN1229279C - 一种碳纳米管阵列结构及其制备方法 - Google Patents
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Abstract
本发明揭示一种碳纳米管阵列结构,其包括一基底、形成于基底上的催化剂层、以及从催化剂层上长出的碳纳米管阵列,该碳纳米管阵列具有向一方向弯曲的特性。本发明提供的碳纳米管阵列具有向一预定的方向弯曲,丰富碳纳米管器件设计的多样性,为碳纳米管器件的设计提供更多的选择空间。本发明同时还揭示了一种制备上述碳纳米管阵列结构的方法。其步骤包括:(1)在基底的表面形成一催化剂层,该催化剂层的厚度均匀一致;(2)在催化剂层上沉积一层影响碳纳米管长生速度的材料;(3)在含氧气氛中退火,使催化剂层氧化成为纳米级催化剂颗粒;(4)通入碳源气,生长碳纳米管。
Description
【技术领域】
本发明关于一种碳纳米管阵列结构及其制备方法。
【背景技术】
由于碳纳米管独特的电学性质,其在纳米集成电路、单分子器件等领域的应用有着不可估量的前景。目前人们已经能够在实验室里少量制造基于碳纳米管的场效应管、逻辑器件及存储器件等,并研究了它的性质,具体请参阅Sander J Tans等人1998年发表在Nature 393-49,Room-temperature transistorbased on a single carbon nanotube一文。但大规模的制备和具有实际意义的应用则必须求助于由下而上(Bottom Up)的制备工艺。
由下而上的制备工艺要求能够对碳纳米管的生长位置、方向、大小、长短、甚至碳纳米管的螺旋度进行必要的控制,通过少量而经济的步骤直接生长出所需要的器件结构。范守善等人在Science 283,512-514(1999),Self-oriented regular arrays of carbon nanotubes and their field emissionproperties一文中,以及Z.F.Ren等人在Science 282,1105-1107(Nov 6,1998),Synthesis of large arrays of well-aligned carbon nanotubes on glass一文中均揭露了一种通过催化剂图形(Patterned Catalyst)来控制碳纳米管的生长位置及使其垂直于基底的生长方法。
另外,B.Q.Wei等人在Nature 416,495-496(Apr 4,2002),Organizedassembly of carbon nanotubes一文中揭露了一种可以通过对基底形状的设计实现碳纳米管在三维基底上生长出垂直于各处表面的生长方法。
但是上述方法中所获得的碳纳米管阵列均垂直于生长的基底,无法对阵列的生长方向做出控制和改变。
Yuegang Zhang等人在Applied Physics Letters,Vol.79,Number 19,Nov 5,2001,Electric-field-directed growth of aligned single-walled carbon nanotubes一文中揭露了一种通过电场控制碳纳米管的生长方向的方法,在电场的作用下,可控制奈米碳管沿电场方向生长。
但是上述方法中,用电场控制碳纳米管生长方向的方法则会加重器件设计的复杂程度,而且由于电场本身的广域性,难以实现对局部多种生长方向的控制。这些因素都限制了碳纳米管器件设计的多样化和实用性,因此,发明一种不需外场的局部碳纳米管生长方向控制方法实为必要。
【发明内容】
本发明要解决的一个技术问题是提供一种向一特定方向弯曲的碳纳米管阵列结构。
本发明解决的另一个技术问题是提供一种制造上述碳纳米管阵列结构的方法。
为解决上述技术问题,本发明揭示一碳纳米管阵列结构,包括一基底、形成于基底上的催化剂合金颗粒及从催化剂合金颗粒上长出的碳纳米管阵列,该催化剂合金颗粒中含有影响碳纳米管长生速度材料,该材料的含量沿一方向渐变,该碳纳米管阵列向一特定方向弯曲。
本发明同时还揭示制备上述碳纳米管阵列结构的方法。其步骤包括:
(1)提供一基底;
(2)在基底的表面形成催化剂图形;
(3)在催化剂图形上沉积一层影响碳纳米管生长速度的材料;
(4)在含氧气氛中退火,使催化剂层氧化成为纳米级催化剂颗粒;
(5)通入碳源气,生长碳纳米管。
此前的现有技术中碳纳米管阵列均是垂直于基底,本发明提供的碳纳米管阵列具有向一预定的方向弯曲,丰富碳纳米管器件设计的多样性,为碳纳米管器件的设计提供更多的选择空间。
与现有的碳纳米管阵列的生长方法相比,本发明提供的方法仅在催化剂层上多沉积一层影响碳纳米管长生速度的材料,通过控制材料厚度的变化和分布,实现在基底的不同位置碳纳米管有不同的长生速度,因碳纳米管之间有范德华兹力的影响,使得碳纳米管阵列在生长过程中向一特定方向弯曲。其中影响碳纳米管长生速度材料的厚度调制是决定图形上生长的碳纳米管阵列弯曲形状的主要因素。
【附图说明】
图1是本发明中沉积有催化剂薄膜的基底示意图。
图2是图1所示基底沉积影响碳纳米管生长速度的材料过程示意图。
图3是本发明中图2所示基底退火后示意图。
图4是本发明中碳纳米管阵列结构的示意图。
【具体实施方式】
请参阅图1,首先提供一基底10,该基底10可选用硅,在该基底10上形成一光阻层11,通过光刻使光阻层11形成预定的图案。在需要生长碳纳米管的位置沉积数纳米厚的催化剂13,催化剂13的厚度为2~9纳米,且厚度需均匀一致,催化剂13的沉积方法可选用热蒸发沉积法、也可选用电子束加热蒸发法等方法配合光刻工艺或图形掩模完成,催化剂13的材料可选有铁、钴、镍或者三种物质任意组合的合金。本实施例选用铁作为催化剂13的材料,其沉积厚度为6纳米。
请参阅图2,在催化剂层薄膜13上沉积一层影响碳纳米管生长速度的材料121,该材料121的厚度由一端向另一端逐渐减薄,本实施方式是通过在光阻11的斜上方放置一材质为铜的直线型蒸发源12,通过热蒸发沉积法,在催化剂13上沉积一层材料121,该材料121厚度渐变分布,其较厚的一端的厚度为8纳米,较薄一端的厚度为3纳米,一般要求较厚一端的厚度不超出10纳米,较薄一端的厚度接近零纳米,上述直线型蒸发源12既可以用沿直线移动的点蒸发源来代替。蒸发也可以选用电子束蒸发等有方向性的沉积方法配合光刻工艺或图形掩模完成,或者利用溶液喷涂配合甩膜、光刻等工艺完成。
请配合参阅图3和图4,洗除光阻层11,将带有催化剂13及材料121的基底10置于空气中,在300℃下退火,使催化剂13氧化,收缩成为纳米级的催化剂颗粒(图未示)。再将其置于反应炉(图未示)中,在保护气体氩气的保护下,通入碳源气乙炔,利用热化学气相沉积法,在600~700℃下生长10分钟,此时催化剂铁与材料铜形成合金颗粒131,在材料121较厚一端合金颗粒131所含的铜较多,在材料121较薄一端合金颗粒131中所含的铜较少,而铜材料121具有减缓碳纳米管生长速度的特性,因材料121较厚一端碳纳米管生长受铜的影响较大,生长较慢,相反,材料121较薄的一端碳纳米管生长相对较快,故,在上述合金颗粒131上生长出的碳纳米管阵列15向材料121较厚一侧弯曲。碳源气也可以选用含碳的其它气体,如乙烯等,保护气体也可为其它气体,如氮气、氢气等。控制生长时间和生长温度则可以控制碳纳米管阵列15的生长高度。
请参阅图4,利用上述方法获得的碳纳米管阵列结构40包括一基底10、形成于基底10上的纳米级合金颗粒131及从合金颗粒131上长出的碳纳米管阵列15,其中合金颗粒131尺寸大小沿一特定方向线性变化,且其铜的含量沿一特定方向也线性变化,该碳纳米管阵列15向一特定方向弯曲。
材料121除了可以是减缓碳纳米管生长速度的铜,也可以是增加碳纳米管生长速度的材料,如钼,如果材料121是加快碳纳米管生长速度的材料,则碳纳米管向材料121较薄一侧弯曲,如果材料121是减缓碳纳米管生长速度的材料,则碳纳米管向材料121较厚一侧弯。
催化剂13的沉积和材料121的沉积顺序可以相互交换,即既可以先沉积催化剂13后沉积材料121,也可以先沉积材料121后沉积催化剂13,材料121的厚度只有几纳米,氧很容易扩散过去,沉积材料121对催化剂13的覆盖不会影响催化剂13的氧化,因而该沉积顺序的交换对碳纳米管阵列15的生长方向控制没有影响。
上述碳纳米管阵列结构可用于平面显示、纳米电子学、大电流场发射电子枪等器件的阴极制造工艺。
Claims (14)
1.一碳纳米管阵列结构,包括一基底、形成于基底上的催化剂合金颗粒及从催化剂合金颗粒上长出的碳纳米管阵列,其特征在于该催化剂合金颗粒中含有影响碳纳米管长生速度材料,该材料的含量沿一方向渐变,该碳纳米管阵列向一特定方向弯曲。
2.如权利要求1所述的碳纳米管阵列结构,其特征在于该基底为硅。
3.如权利要求1所述的碳纳米管阵列结构,其特征在于该影响碳纳米管长生速度材料包含铜或钼。
4.如权利要求1所述的碳纳米管阵列结构,其特征在于该催化剂合金颗粒中的催化剂为铁、钴、镍或者三种物质任意组合的合金之一。
5.一种制备碳纳米管阵列的方法,其特征在于其步骤包括:
(1)提供一基底;
(2)在基底上沉积一催化剂图形;
(3)在催化剂图形上沉积一层影响碳纳米管生长速度的材料;
(4)在含氧气氛中退火,使催化剂层氧化成为纳米级催化剂颗粒;
(5)通入碳源气,生长碳纳米管。
6.如权利要求5所述制备碳纳米管阵列的方法,其特征在于该基底为硅。
7.如权利要求5所述制备碳纳米管阵列的方法,其特征在于该催化剂层可以为铁、钴、镍或者三种物质任意组合的合金之一。
8.如权利要求5述制备碳纳米管阵列的方法,特征在于催化剂层的厚度一致,在2~9纳米之间。
9.如权利要求5所述制备碳纳米管阵列的方法,其特征在于该影响碳纳米管生长速度的材料包含铜或钼。
10.如权利要求5所述制备碳纳米管阵列的方法,其特征在于该影响碳纳米管生长速度的材料的厚度为一渐变分布。
11.如权利要求10所述制备碳纳米管阵列的方法,其特征在于该影响碳纳米管生长速度材料的较厚一端的厚度不超过10纳米,较薄一端的厚度大于零纳米。
12.如权利要求5所述制备碳纳米管阵列的方法,其特征在于沉积影响碳纳米管生长速度材料的方法可为热蒸发沉积法或电子束蒸发法或溶液喷涂甩膜方法来完成。
13.如权利要求12所述制备碳纳米管阵列的方法,其特征在于热蒸发沉积法的蒸发源为直线型蒸发源或沿直线移动点蒸发源。
14.如权利要求5所述制备碳纳米管阵列的方法,其特征在于步骤(3)在步骤(2)前进行。
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US10/640,340 US7161286B2 (en) | 2002-12-05 | 2003-08-12 | Carbon nanotube array and method for making same |
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GB0226590D0 (en) * | 2002-11-14 | 2002-12-24 | Univ Cambridge Tech | Method for producing carbon nanotubes and/or nanofibres |
US6933222B2 (en) * | 2003-01-02 | 2005-08-23 | Intel Corporation | Microcircuit fabrication and interconnection |
US7129097B2 (en) * | 2004-07-29 | 2006-10-31 | International Business Machines Corporation | Integrated circuit chip utilizing oriented carbon nanotube conductive layers |
CN100467367C (zh) * | 2004-08-11 | 2009-03-11 | 清华大学 | 碳纳米管阵列结构及其制备方法 |
CN100582032C (zh) * | 2004-12-08 | 2010-01-20 | 鸿富锦精密工业(深圳)有限公司 | 模造玻璃透镜模仁 |
JP4481853B2 (ja) * | 2005-03-18 | 2010-06-16 | 富士通株式会社 | カーボンナノチューブデバイスの製造方法 |
CN100436310C (zh) | 2005-07-13 | 2008-11-26 | 清华大学 | 碳纳米管阵列制作方法 |
CN100436311C (zh) * | 2005-07-22 | 2008-11-26 | 清华大学 | 碳纳米管阵列制作方法 |
CN100462301C (zh) * | 2005-12-09 | 2009-02-18 | 清华大学 | 一种碳纳米管阵列的制备方法 |
WO2007092770A2 (en) | 2006-02-02 | 2007-08-16 | William Marsh Rice University | Fabrication de dispositifs electriques par façonnage de nanotubes |
JP4979296B2 (ja) * | 2006-08-02 | 2012-07-18 | 富士通株式会社 | カーボンナノチューブの製造方法 |
EP1936666A1 (en) * | 2006-12-22 | 2008-06-25 | Interuniversitair Microelektronica Centrum | Doping of nanostructures |
CN101409961B (zh) * | 2007-10-10 | 2010-06-16 | 清华大学 | 面热光源,其制备方法及应用其加热物体的方法 |
CN101409962B (zh) * | 2007-10-10 | 2010-11-10 | 清华大学 | 面热光源及其制备方法 |
CN101400198B (zh) * | 2007-09-28 | 2010-09-29 | 北京富纳特创新科技有限公司 | 面热光源,其制备方法及应用其加热物体的方法 |
JP2009155693A (ja) * | 2007-12-27 | 2009-07-16 | Sonac Kk | 基板ユニット |
US20100122980A1 (en) * | 2008-06-13 | 2010-05-20 | Tsinghua University | Carbon nanotube heater |
US20100126985A1 (en) * | 2008-06-13 | 2010-05-27 | Tsinghua University | Carbon nanotube heater |
US20100000669A1 (en) * | 2008-06-13 | 2010-01-07 | Tsinghua University | Carbon nanotube heater |
US20100274312A1 (en) * | 2009-04-22 | 2010-10-28 | Konstantinos Alataris | Spinal cord modulation for inducing paresthetic and anesthetic effects, and associated systems and methods |
CN101857461B (zh) * | 2010-06-15 | 2012-05-30 | 清华大学 | 一种半导体碳纳米管阵列的制备方法 |
CN112358855B (zh) * | 2020-10-26 | 2021-12-28 | 深圳烯湾科技有限公司 | 碳纳米管导热片及其制备方法 |
CN113046719B (zh) * | 2021-03-16 | 2023-04-18 | 江苏集萃脑机融合智能技术研究所有限公司 | 确定二维材料生长合金催化剂中金属原子最佳配比的方法 |
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