Growth of all-carbon horizontally aligned single-walled carbon nanotubes nucleated from fullerene-based structures
© Ibrahim et al.; licensee Springer. 2013
Received: 16 November 2012
Accepted: 5 April 2013
Published: 6 June 2013
All-carbon single-walled carbon nanotubes (SWCNTs) were successfully synthesized, nucleated using a fullerene derivative. A systematic investigation into the initial preparation of C60 fullerenes as growth nucleators for the SWCNTs was conducted. Enhancement in the yield of the produced SWCNT has been achieved with exploring different dispersing media for the fullerenes, the period, and environment of the initial thermal treatment of the fullerenes in addition to the use of different fullerene-based structures. The systematic studies significantly advance our understanding of the growth of the all-carbon catalyst-free single-walled carbon nanotubes. Field-effect transistors were fabricated using the catalyst-free SWCNT and then electrically characterized, showing current capacity as high as the well-studied catalyst-assisted nanotubes.
KeywordsHorizontally aligned SWCNT CVD Catalyst-free SWCNT Fullerene nucleate CNT
Enormous efforts have been invested towards the realization of single-walled carbon nanotube (SWCNT)-based products due to their extraordinary properties [1, 2]. One of the more attractive potential applications of these exciting nanostructures is as a building block for nanoelectronics. To this end, individual or parallel-aligned SWCNTs with tunable yield are important [3, 4]. For such applications, however, the reproducible control of the nanotubes’ spatial orientation and chiral management still require further development . Some success has been achieved regarding the controlled fabrication of well-oriented nanotubes, especially when directly fabricating aligned tubes using chemical vapor deposition (CVD) [6, 7]. Usually though, a catalyst particle (mostly metal catalyst particles) are used to nucleate the growth of the nanotubes, and this has a drawback since the catalyst particles may diffuse into the substrate or tube and thus affect their intrinsic properties or that of a device built around them [8, 9]. Therefore, the synthesis of a catalyst-free-aligned SWCNT is very attractive. Different all-carbon routes have been developed, for example, using diamonds as open-ended SWNT and fullerenes as SWCNT nucleators [10–12]. However, the yield of the grown tubes is generally low. Moreover, this remains a very limited understanding of all-carbon SWCNT growth.
In this study, we systematically investigate aspects related to yield from metal-free horizontally oriented SWCNTs nucleated from pristine C60 fullerenes and exohedrally functionalized C60F18 fullerenes. Aside from direct comparisons between the two types of fullerenes, we also investigate the role of the dispersing solution and pretreatment steps to functionalize and activate them prior to CVD growth.
Nominal amounts of fullerene derivatives (C60 and C60F18), which will later serve as nanotube nucleators, were homogenously dispersed independently in toluene, acetone, and ethanol by overnight ultrasonication. Single crystal quartz substrates (10 × 10 × 0.5 mm, angle cut 38° 00’, single side polished from Hoffman Materials, LLC, Carlisle PA, USA), were initially subjected to thermal annealing in air at 750°C for 15 min prior to the chemical vapor deposition (CVD) reaction for nanotube growth. This results in a smoother surface which helps provide higher yields . The initial fullerenes were then placed on the quartz substrate prior to these treatments by drop coating the dispersed fullerenes. The deposited fullerenes are opened (to form open caps that serve as nucleation centers) and then activated by functionalization. These processes are accomplished by first heating the loaded substrates in various environments (air, synthetic air, Ar or H2) for different periods (10 to 120 min) at temperatures between 400°C and 500°C in a 1-in purpose-built horizontal tube furnace. Thereafter, the activation is achieved by heating the samples at 900°C in water vapor (0.17 standard liter per minute (SLPM) Ar bubbled through water) for 2 min and then heating in hydrogen (0.75 SLPM) for the next 3 min. Later, the CVD reaction was performed in a gaseous environment of hydrogen (4.5 SLPM), Ar (0.2 SLPM), and Ar (0.32 SLPM) bubbled through ethanol, keeping the temperature stable at 900°C for 20 min.
Atomic force microscopy (Digital Instruments NanoScope IIIa, Veeco, Plainview, NY, USA) operating in the tapping mode was employed to characterize the fullerenes after the different treatment steps and also assess the yield and diameter of the nanotubes after CVD growth. The length and alignment of the CNTs were determined using a scanning electron microscope (SEM; NOVA 200 NanoSEM, FEI, Hillsboro, OR, USA; with typical acceleration voltage of 2 to 3 kV), while the type and quality of the grown tubes were estimated by transmission electron microscopy (a double Cs-Corrected JEM-2010 F, JEOL, Akishima-shi, Japan; using an acceleration voltage of 80 kV) and Raman spectroscopy (DXR SmartRaman Thermo Scientific, Waltham, MA, USA; λ = 533 nm). For the electrical measurements, a set of source-drain electrode pairs (10 nm Cr, 40 nm Au) in addition to the gate electrode (50 nm Al2O3, 10 nm Cr, 40 nm Au) were fabricated using standard e-beam lithography on the substrates where the nanotubes were as-grown.
Results and discussion
In summary, we have systematically investigated the pretreatment steps and growth of catalyst-free grown carbon nanotubes using opened and functionalized C60 and C60F18 as nucleation centers. The choice of dispersion agent is also important such that large clusters of initially deposited fullerenes lead to improved yields. Optimizing the thermal treatment steps to open and functionalize the fullerene clusters are also shown to improve the yield of the grown nanotubes. The as-synthesized tubes appear to be predominantly SWCNT. The high performance of the field-effect transistors fabricated using such catalyst-free SWCNTs make such tubes as promising candidates for future nanoelectronic applications.
II thanks the DAAD; GC acknowledges support from the South Korean Ministry of Education, Science, and Technology Program, Project WCU ITCE no. R31-2008-000-10100-0; and MHR thanks the EU (ECEMP) and the Freistaat Sachsen.
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