Liu Xi, Bigioni Terry P, Xu Yuan, Cassell Alan M, Cruden Brett A
J Phys Chem B. 2006 Oct 19;110(41):20102-6. doi: 10.1021/jp0647378.
We have grown a dense array of vertically aligned carbon nanotubes (CNTs) with a controlled distribution of diameters by using block copolymer micelles to form and pattern catalyst particles. The block copolymer poly(styrene-block-acrylic acid) (PS16500-PAA4500) was dissolved in toluene to form micelles and then loaded with FeCl3. The metal-loaded micelles were spin-coated on Si and then thermally treated to remove the polymer. Using this process, we produced surfaces patterned with iron oxide catalyst particles with particle densities ranging from 1400 microm(-2) to 3800 microm(-2) and a size distribution of (6.9 +/- 0.8) nm. CNT growth by thermal chemical vapor deposition was then performed on these samples. The low-density catalyst sample produced unaligned, low-density CNTs, whereas the high-density catalyst sample produced vertically aligned, dense CNTs about 10 microm in length. Transmission electron microscopy revealed that the CNTs typically had double and triple graphitic layers with normally distributed diameters of (4.5 +/- 1.1) nm. For comparison, CNTs grown from the standard approach of blanket Fe films had a wide distribution of diameters between 6 and 21 nm. This catalyst preparation approach dramatically sharpens the size distribution of CNTs, compared to standard approaches, and provides a simple means of controlling the areal density of CNTs.
我们通过使用嵌段共聚物胶束来形成和图案化催化剂颗粒,生长出了直径分布可控的密集垂直排列碳纳米管(CNT)阵列。将嵌段共聚物聚(苯乙烯 - 丙烯酸)(PS16500 - PAA4500)溶解在甲苯中形成胶束,然后负载FeCl3。将负载金属的胶束旋涂在硅上,然后进行热处理以去除聚合物。通过这个过程,我们制备出了表面带有氧化铁催化剂颗粒的图案,颗粒密度范围为1400微米^(-2)至3800微米^(-2),尺寸分布为(6.9±0.8)纳米。然后在这些样品上通过热化学气相沉积法进行CNT生长。低密度催化剂样品产生了无序、低密度的CNT,而高密度催化剂样品产生了长度约为10微米的垂直排列、密集的CNT。透射电子显微镜显示,这些CNT通常具有双层和三层石墨层,直径呈正态分布,为(4.5±1.1)纳米。作为对比,采用标准的覆盖铁膜方法生长的CNT直径分布在6至21纳米之间,范围很宽。与标准方法相比,这种催化剂制备方法显著锐化了CNT的尺寸分布,并提供了一种控制CNT面密度的简单方法。