Multi-Directional Growth of Aligned Carbon Nanotubes Over Catalyst Film Prepared by Atomic Layer Deposition
© The Author(s) 2010
Received: 18 May 2010
Accepted: 12 June 2010
Published: 23 June 2010
The structure of vertically aligned carbon nanotubes (CNTs) severely depends on the properties of pre-prepared catalyst films. Aiming for the preparation of precisely controlled catalyst film, atomic layer deposition (ALD) was employed to deposit uniform Fe2O3 film for the growth of CNT arrays on planar substrate surfaces as well as the curved ones. Iron acetylacetonate and ozone were introduced into the reactor alternately as precursors to realize the formation of catalyst films. By varying the deposition cycles, uniform and smooth Fe2O3 catalyst films with different thicknesses were obtained on Si/SiO2 substrate, which supported the growth of highly oriented few-walled CNT arrays. Utilizing the advantage of ALD process in coating non-planar surfaces, uniform catalyst films can also be successfully deposited onto quartz fibers. Aligned few-walled CNTs can be grafted on the quartz fibers, and they self-organized into a leaf-shaped structure due to the curved surface morphology. The growth of aligned CNTs on non-planar surfaces holds promise in constructing hierarchical CNT architectures in future.
Vertically aligned carbon nanotube (CNT) arrays were composed of aligned CNTs and possessed outstanding performances in materials science, catalysis, optics, electrics, and energy conversion/storage. Numerous functional applications, such as nano-brushes, field emitters, catalyst and catalyst supports, electronic electrodes, shock absorbing, energy conversion and storage, have been proposed [1–5]. The performance of aligned CNTs depends highly on the intrinsic structure of CNTs as well as the organization of CNTs. For example, large specific surface area (small CNT diameter and wall number) and suitable pore size distribution (hierarchical array structures) were required for the application of aligned CNT arrays in supercapacitor . Therefore, the modulations of the CNT structure and their organization were of common interest in the research of CNT arrays.
Precisely controlled catalyst layers were widely used to modulate the metal catalyst particle size and therefore the structure of CNTs in the arrays. Generally, thin catalyst film favored the synthesis of CNTs with few walls. Physical vapor deposition (PVD, such as electron beam evaporation and magnetic sputtering) was one of the most popular methods for the deposition of uniform catalyst films on substrates [1, 7–9]. The wall number distribution of CNTs has been successfully controlled by modulating the thicknesses of Fe catalyst films . Some endeavors on modulating the CNT structure by delicately controlled growth parameters were also made . However, it must be noticed that, up to now, precise deposition of metal catalyst film on a non-planar surface was still difficult. Therefore, it is hard to synthesize aligned few-walled CNTs on a non-planar surface , which brings difficulties in constructing multi-stage aligned CNTs on non-planar substrates.
On the other hand, CNT arrays can be facilely synthesized on non-planar surfaces through floating catalyst chemical vapor deposition (CVD) . Catalyst particles were in situ formed on substrates during the growth process of aligned CNTs [12–14]. Various functional materials with complex structures, such as CNT flowers [12, 15], CNT brushes [2, 16–18], CNT polyhedrons , CNT tubes [20, 21], have been fabricated. However, the catalyst particles formed by the decomposition of catalyst precursor were easily agglomerated into large ones and this gave rise to CNT arrays composed of large-diameter multi-walled CNTs (with diameters mainly in the range of 10–200 nm) . Consequently, the as-obtained aligned CNTs were with limited specific surface area (lower than 200 m2/g). This is still an obstacle for the further applications of hierarchical CNTs. Under the state-of-the-art of CNT array synthesis, the construction of multi-stage CNT arrays composed of thin CNTs on non-planar surface was still an obstacle. Considering the hardness in controlling catalyst sizes during floating catalyst process, a method for the uniform coating of catalysts on non-planar substrate should be developed.
Recently, atomic layer deposition (ALD) has become an important way to fabricate thin film on various substrates. It is a thin film growth method based on sequential, self-limiting surface reactions that can deposit conformal thin films with excellent conformal step coverage and is ideal for the deposition on complex non-planar surface topography [22, 23]. It is a powerful tool to fabricate thin film on irregular or porous substrate. For instance, Liu et al. reported the deposition of platinum nanoparticles on CNTs by ALD for the application in proton-exchange membrane fuel cells ; ALD was also employed to grow coaxial thin films of Al2O3, V2O5, TiO2, HfO2, [26, 27], and Al2O3/W bilayers  on CNTs. Recently, Amama et al. reported the preparation of alumina layer as Fe catalyst support through ALD process for CNT growth. It should be noticed that the metal film was still prepared by electron beam evaporation . Direct fabrication of metal catalyst film served as active phase for CNT growth is still an open question.
During ALD process, iron source was imported into the reactor and a self-terminating reaction occurred on the substrate surface. After a purging of inert gas N2 to remove the non-reacted reactants and gaseous by-products, monolayer iron compounds were adsorbed. As ozone oxidized the iron compounds, monolayer iron oxides were obtained during a cycle. After a purge to evacuate ozone and by-products, the deposition process continued next cycle, and the thicknesses of Fe2O3 films were controlled by varying the reaction cycles. After the deposition of catalysts, the substrates were transferred into tubular furnace and annealed under hydrogen atmosphere to reduce iron oxides into Fe catalysts. The CVD process was then conducted for the growth of aligned few-walled CNTs. Since the catalyst films were deposited on all the surfaces exposed to the gaseous precursors in ALD process, few-walled CNT arrays can radially grow on fibrous substrates.
Preparation of Catalyst Film by ALD Method
Silicon wafer (with 700 nm SiO2 layer) coated with 10-nm-thick Al2O3 by e-beam evaporation and quartz fibers with a diameter of about 10 μm were employed as substrates for ALD deposition. The iron source was Fe(acac)3 (iron(III) acetylacetonate, Alfar, >99.99%) and ozone served as oxidants was supplied from an ozone generator with oxygen (Beiwen Gas, purity >99.999%) as input. The output ozone concentration is 7 vol%. N2 was used as both carrier gas for iron source and the purge gas for ALD deposition.
Thin catalyst films were deposited in a 3 L vacuum chamber. The precursors (iron sources and oxidants) were pulsed alternately into the reactor, separated by N2 gas purge (purity > 99.999%) to realize the ALD deposition. The films were deposited at a pressure of about 100–500 Pa in the temperature of 230°C. The iron source was sublimed at 80°C and carried into the reactor by N2. Each ALD cycle consisted of 100-s Fe(acac)3 pulse, 3-s N2 purge pulse, 10-s ozone pulse, and 3-s N2 purge pulse. Various cycles of ALD deposition were conducted on both wafer and quartz fiber to obtain Fe2O3 catalyst films.
Synthesis of Aligned CNTs on ALD Catalysts
Substrates were transferred into horizontal quartz-tube-reactor set in a tube furnace for the CVD synthesis of aligned CNTs. The temperature of the reactor increased to 750°C under the protection of Ar and H2. C2H4 together with CO2 was then introduced to realize the growth of CNT arrays. The typical flow rates of Ar, H2, C2H4, and CO2 were 250, 200, 100, and 50 sccm, respectively. After a 1-h growth of aligned CNTs, the feedstock of C2H4 and CO2 was terminated, and the reactor was cooled down under the protection of Ar and H2.
The catalyst layers deposited by ALD process were characterized with X-ray photoelectron spectroscopy (XPS, PHI Quantera SXM) and atomic force microscope (AFM, Nanoman VS). High-resolution scanning electron microscopy (SEM, JSM 7401F operating at 5.0 kV) was used to characterize the morphology of the CNT arrays. High-resolution transmission electron microscopy (TEM, JEM 2010 operating at 120.0 kV) was used to determine the detailed structure of the CNTs in the arrays. Raman spectroscopy of the CNTs was performed using a Raman microscope (Renishaw, RM2000, He–Ne laser excitation line 633.0 nm).
Results and Discussion
TEM characterization was performed to determine the detailed structure of CNTs in the arrays. Figure 3d is the typical low-magnification TEM image of the CNTs derived on the substrate with 40 ALD cycles of Fe2O3 deposition. The samples mainly consisted of few-walled CNTs. Figure 3e showed a triple-walled CNT with an outer diameter of 8.7 nm. Based on the statistic results, CNTs obtained with different ALD cycles for Fe2O3 deposition showed outer diameters ranging from 7 to 12 nm and wall numbers of 3-6. The top part of CNT arrays with different ALD cycles was further examined by Raman spectroscopy (Fig. 3f). The Raman spectra showed two main peaks: D peak around 1,325 cm−1 and G peak around 1,580 cm−1, corresponding to the signal of disordered and ordered graphite structures. Therefore, the intensity ratio of G peak to D peak was widely used in determining the graphitization degree of CNTs. As calculated, the I G/I D ratio kept at about 0.72 for the CNTs derived on substrate with 10- to 30-ALD cycle catalyst film. The relatively low I G/I D ratio may be attributed to the large diameters and high defect densities of the CNTs . The I G/I D ratio decreased to 0.58 for the CNT arrays obtained on substrates with 40 ALD cycles, which can be attributed to higher surface roughness and the non-uniform catalyst particles.
The ALD process for the deposition of catalyst films realized the synthesis of few-walled CNT arrays on multi-shaped substrate. As demonstrated by the quartz fibers, CNT arrays can radially grow on the fibers, which may find applications in the reinforcement in various cloths of fibers by CNTs [16, 32]. The growth of long CNT arrays may realize the multi-stage weaving of CNTs and the original fibers to construct 3D CNT architectures. Furthermore, it should be noticed that the leaf-like growth mode exposed the substrate (the catalyst particles) to the reaction atmosphere. The normally considered diffusion limitation and stress-induced deactivation for CNT arrays growth no longer existed, which provides an access to the formation of ultra-long aligned CNTs. The introduction of ALD in the synthesis of CNTs may bring applications in hierarchical electrode materials, micro-channel catalyst supports, pore-structure-designed membranes for multi-functional materials, catalysis, and energy conversion/storage [1, 4, 35].
ALD process was introduced for the preparation of uniform catalyst films for aligned CNT growth. With various ALD cycles, Fe2O3 films with different thicknesses were coated onto the substrate and supported the growth of few-walled CNT arrays. When on flat substrate, such as Si wafer, large area uniform aligned CNTs were fabricated, while aligned CNTs radially grew and self-organized into leaf-like structures on quartz fibers. Benefiting from the advantages in the precise control of film thickness and ability for coating substrate with complicated structures, ALD process holds potential applications for building up hierarchical CNT structures in future.
The work was supported by the National Natural Science Foundation of China (Nos. 20736007, and 2007AA03Z346) and the China National Basic Research Program (No. 2006CB0N0702). We thank Prof. Dezheng Wang for his great help in the construction of ALD reaction chamber.
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- Fan SS, Chapline MG, Franklin NR, Tombler TW, Cassell AM, Dai HJ: Science. 1999, 283: 512. ;COI number [1:CAS:528:DyaK1MXoslagtA%3D%3D]; Bibcode number [1999Sci...283..512F] 10.1126/science.283.5401.512View ArticleGoogle Scholar
- Cao AY, Veedu VP, Li XS, Yao ZL, Ghasemi-Nejhad MN, Ajayan PM: Nat. Mater.. 2005, 4: 540. ; COI number [1:CAS:528:DC%2BD2MXlvFOisro%3D]; Bibcode number [2005NatMa...4..540C] 10.1038/nmat1415View ArticleGoogle Scholar
- Zhang J, Liu X, Blume R, Zhang AH, Schlogl R, Su DS: Science. 2008, 322: 73. ;COI number [1:CAS:528:DC%2BD1cXhtFyhurfP]; Bibcode number [2008Sci...322...73Z] 10.1126/science.1161916View ArticleGoogle Scholar
- Pan H, Li JY, Feng YP: Nanoscale Res. Lett.. 2010, 5: 654. ; COI number [1:CAS:528:DC%2BC3cXkslelsLo%3D]; Bibcode number [2010NRL.....5..654P] 10.1007/s11671-009-9508-2View ArticleGoogle Scholar
- Zhang Q, Zhao MQ, Liu Y, Cao AY, Qian WZ, Lu YF, Wei F: Adv. Mater.. 2009, 21: 2876.COI number [1:CAS:528:DC%2BD1MXptlCiu7s%3D] 10.1002/adma.200900123View ArticleGoogle Scholar
- Hiraoka T, Izadi-Najafabadi A, Yamada T, Futaba DN, Yasuda S, Tanaike O, Hatori H, Yumura M, Iijima S, Hata K: Adv. Funct. Mater.. 2010, 20: 422.COI number [1:CAS:528:DC%2BC3cXhslWhurg%3D] 10.1002/adfm.200901927View ArticleGoogle Scholar
- Hata K, Futaba DN, Mizuno K, Namai T, Yumura M, Iijima S: Science. 2004, 306: 1362. ; COI number [1:CAS:528:DC%2BD2cXpvVektbg%3D]; Bibcode number [2004Sci...306.1362H] 10.1126/science.1104962View ArticleGoogle Scholar
- Pint CL, Alvarez NT, Hauge RH: Nano Res.. 2009, 2: 526.COI number [1:CAS:528:DC%2BD1MXhtV2jtb7E] 10.1007/s12274-009-9050-7View ArticleGoogle Scholar
- Chakrabarti S, Kume H, Pan LJ, Nagasaka T, Nakayama Y: J. Phys. Chem. C. 2007, 111: 1929.COI number [1:CAS:528:DC%2BD2sXltleluw%3D%3D] 10.1021/jp0666986View ArticleGoogle Scholar
- Huang JQ, Zhang Q, Zhao MQ, Wei F: Nano Res.. 2009, 2: 872.COI number [1:CAS:528:DC%2BD1MXhsVCjt7fK] 10.1007/s12274-009-9088-6View ArticleGoogle Scholar
- Kim HS, Kim B, Lee B, Chung H, Lee CJ, Yoon HG, Kim W: J. Phys. Chem. C. 2009, 113: 17983.COI number [1:CAS:528:DC%2BD1MXhtFyqsrbO] 10.1021/jp9078162View ArticleGoogle Scholar
- Zhang Q, Huang JQ, Zhao MQ, Qian WZ, Wang Y, Wei F: Carbon. 2008, 46: 1152.COI number [1:CAS:528:DC%2BD1cXmvVOnt78%3D] 10.1016/j.carbon.2008.04.017View ArticleGoogle Scholar
- Cui TX, Lv RT, Kang FY, Hu Q, Gu JL, Wang KL, Wu DH: Nanoscale Res. Lett.. 2010, 5: 941. ; COI number [1:CAS:528:DC%2BC3cXmvFelurw%3D]; Bibcode number [2010NRL.....5..941C] 10.1007/s11671-010-9586-1View ArticleGoogle Scholar
- Lv RT, Kang FY, Zhu D, Zhu YQ, Gui XC, Wei JQ, Gu JL, Li DJ, Wang KL, Wu DH: Carbon. 2009, 47: 2709.COI number [1:CAS:528:DC%2BD1MXotl2hur0%3D] 10.1016/j.carbon.2009.05.027View ArticleGoogle Scholar
- He DL, Bozlar M, Genestoux M, Bai JB: Carbon. 2010, 48: 1159.COI number [1:CAS:528:DC%2BC3cXnt1aktg%3D%3D] 10.1016/j.carbon.2009.11.039View ArticleGoogle Scholar
- Zhang Q, Qian WZ, Xiang R, Yang Z, Luo GH, Wang Y, Wei F: Mater. Chem. Phys.. 2008, 107: 317.COI number [1:CAS:528:DC%2BD2sXhsVejsLnO] 10.1016/j.matchemphys.2007.07.020View ArticleGoogle Scholar
- Konig K, Novak S, Ivekovic A, Rade K, Meng DC, Boccaccini AR, Kobe S: J. Eur. Ceram. Soc.. 2010, 30: 1131.COI number [1:CAS:528:DC%2BC3cXmvValtw%3D%3D] 10.1016/j.jeurceramsoc.2009.07.027View ArticleGoogle Scholar
- Qian H, Bismarck A, Greenhalgh ES, Shaffer MSP: Carbon. 2010, 48: 277.COI number [1:CAS:528:DC%2BD1MXhtlWlsbbI] 10.1016/j.carbon.2009.09.029View ArticleGoogle Scholar
- Qu JY, Zhao ZB, Qiu JS, Gogotsi Y: Chem. Commun.. 2008., 2747: Google Scholar
- Qu JY, Zhao ZB, Wang ZY, Wang XZ, Qiu JS: Carbon. 2010, 48: 1465.COI number [1:CAS:528:DC%2BC3cXhs1KitrY%3D] 10.1016/j.carbon.2009.12.041View ArticleGoogle Scholar
- Zhao ZB, Qu JY, Qiu JS, Wang XZ, Wang ZY: Chem. Commun.. 2006., 594: Google Scholar
- Knez M, Niesch K, Niinisto L: Adv. Mater.. 2007, 19: 3425.COI number [1:CAS:528:DC%2BD2sXhtlKktbjJ] 10.1002/adma.200700079View ArticleGoogle Scholar
- George SM: Chem. Rev.. 2010, 110: 111.COI number [1:CAS:528:DC%2BD1MXhsV2hurjJ] 10.1021/cr900056bView ArticleGoogle Scholar
- Liu C, Wang CC, Kei CC, Hsueh YC, Perng TP: Small. 2009, 5: 1535.COI number [1:CAS:528:DC%2BD1MXos1Cqt78%3D] 10.1002/smll.200900278View ArticleGoogle Scholar
- Cavanagh AS, Wilson CA, Weimer AW, George SM: Nanotechnology. 2009, 20: 255602. Bibcode number [2009Nanot..20y5602C] 10.1088/0957-4484/20/25/255602View ArticleGoogle Scholar
- Willinger MG, Neri G, Rauwel E, Bonavita A, Micali G, Pinna N: Nano Lett.. 2008, 8: 4201. ; COI number [1:CAS:528:DC%2BD1cXhtlSqtbvF]; Bibcode number [2008NanoL...8.4201W] 10.1021/nl801785bView ArticleGoogle Scholar
- Willinger MG, Neri G, Bonavita A, Micali G, Rauwel E, Herntrich T, Pinna N: Phys. Chem. Chem. Phys.. 2009, 11: 3615.COI number [1:CAS:528:DC%2BD1MXlsFWgtb4%3D] 10.1039/b821555cView ArticleGoogle Scholar
- Amama PB, Pint CL, Kim SM, McJilton L, Eyink KG, Stach EA, Hauge RH, Maruyama B: ACS Nano. 2010, 4: 895.COI number [1:CAS:528:DC%2BC3cXhsFagtL8%3D] 10.1021/nn901700uView ArticleGoogle Scholar
- de los Arcos T, Garnier MG, Oelhafen P, Mathys D, Seo JW, Domingo C, Garci-Ramos JV, Sanchez-Cortes S: Carbon. 2004, 42: 187. 10.1016/j.carbon.2003.10.020View ArticleGoogle Scholar
- Kpetsu JBA, Jedrzejowski P, Cote C, Sarkissian A, Merel P, Laou P, Paradis S, Desilets S, Liu H, Sun XL: Nanoscale Res. Lett.. 2010, 5: 539. ; COI number [1:CAS:528:DC%2BC3cXkslelsro%3D]; Bibcode number [2010NRL.....5..539K] 10.1007/s11671-010-9544-yView ArticleGoogle Scholar
- Garcia-Cespedes J, Thomasson S, Teo KBK, Kinloch IA, Milne WI, Pascual E, Bertran E: Carbon. 2009, 47: 613.COI number [1:CAS:528:DC%2BD1MXhtlSgurs%3D] 10.1016/j.carbon.2008.10.045View ArticleGoogle Scholar
- Yamamoto N, Hart AJ, Garcia EJ, Wicks SS, Duong HM, Slocum AH, Wardle BL: Carbon. 2009, 47: 551.COI number [1:CAS:528:DC%2BD1MXhtlSgtbc%3D] 10.1016/j.carbon.2008.10.030View ArticleGoogle Scholar
- Garcia EJ, Wardle BL, Hart AJ, Yamamoto N: Compos. Sci. Technol.. 2008, 68: 2034.COI number [1:CAS:528:DC%2BD1cXms1ygsbc%3D] 10.1016/j.compscitech.2008.02.028View ArticleGoogle Scholar
- Zhang QH, Liu JW, Sager R, Dai LM, Baur J: Compos. Sci. Technol.. 2009, 69: 594.COI number [1:CAS:528:DC%2BD1MXhvFGlsLk%3D] 10.1016/j.compscitech.2008.12.002View ArticleGoogle Scholar
- Su DS, Schlogl R: ChemSusChem. 2010, 3: 136.COI number [1:CAS:528:DC%2BC3cXitF2jtL0%3D] 10.1002/cssc.200900182View ArticleGoogle Scholar