Single-walled Carbon Nanotube Forests Research Articles

Unexpected Efficient Synthesis of Millimeter-Scale Single-Wall Carbon Nanotube Forests Using a Sputtered MgO Catalyst Underlayer Enabled by a Simple Treatment Process.

An unexpected 5000% increase in growth efficiency and high (95%) single-wall selectivity synthesis of vertically aligned carbon nanotubes (CNTs) was shown from Fe catalysts supported on a sputtered MgO underlayer from a simple underlayer treatment, i.e., annealing treatment. In this way, millimeter-scale single-wall carbon nanotube "forests" could be synthesized in a 10 min time, which has never been previously reported for MgO catalyst underlayer or any underlayer besides Al2O3. This level of efficiency and characterized SWCNT properties were similar to those grown using Al2O3 underlayers. Spectroscopic and microscopic analyses revealed that the treatment improved stability of the catalyst nanoparticle array by the suppressing catalyst subsurface diffusion and retaining the metallic state of the surface Fe atoms. Taken together, these results reveal a new route in achieving highly efficient SWCNT synthesis.

Examining the structural contribution to the electrical character of single wall carbon nanotube forest by a height dependent study

We report an electrical investigation of single-wall carbon nanotube (SWCNT) forests where we have succeeded in elucidating the electrical contributions of the forest surface (cap) and vertically aligned (body) structures of the assembly. We applied an electrical characterization method to SWCNT forests patterned into a Hall bar-like configuration to reliably evaluate the lateral (i.e. in-plane) resistance for a series of SWCNT forests spanning three orders of magnitude, 0.3–700 μm, in height while avoiding direct mechanical contact to the measurement region. A simple model based on treating the forests as two parallel resistors was used to explain the observed behavior of the lateral resistivity and forest height. Through this approach we showed that the forests could be described electrically by two structural features, the cap and body. In addition, our analysis found that the resistivity of the body was about 22–720 times higher than that of the cap.

Highly pure, millimeter-tall, sub-2-nanometer diameter single-walled carbon nanotube forests

We report the highly efficient synthesis of sub-2-nm diameter single-walled carbon nanotube (SWCNT) forests with homogenous and controllable diameter (1.5–2.8 nm), millimeter-scale height, and extremely high purity. This control was achieved by combining a previously reported sandwich catalyst (Al/Fe/Al) with an atmospheric synthesis process and the water-assisted thermal chemical vapor deposition method. In this way, a dense array of small and stable catalyst nanoparticles, suitable to support vertical growth, while avoiding gas diffusion limitations, could be prepared from which SWCNT forests could be synthesized efficiently to achieve both high purity and mm-scale height. The mm-tall sub-2-nm diameter SWCNT forests showed good quality (Raman G/D ratio of ∼40) and exceptionally high as-grown purity (outer specific surface area of 1215 m2/g; ideal: 1315 m2/g), which can be directly used without additional post-growth purification process to avoid any potential damage to the CNTs. This result represents a significant advance in synthesizing highly pure, mm-scale length SWCNT forests with sub-2-nm diameters.

CVD Growth of Carbon Nanotube Forest with Selective Wall-Number from Fe–Cu Catalyst

We reported herein the chemical vapor deposition (CVD) growth of vertically aligned carbon nanotubes (CNTs) with selective wall-number using binary Fe–Cu catalysts. High quality single-walled carbon nanotube (SWNT) and double-walled carbon nanotube (DWNT) forests were predominantly produced with selectivity of ∼92% and ∼85%, respectively. Formation of small catalyst nanoparticles with high areal density and fully reduced state was found key for efficient SWNT growth. Characterization of the catalysts by atomic force microanalysis (AFM) and high resolution transmission electron microscope (HRTEM) showed that the introduction of the proper amount of Cu into the Fe/Al2O3 catalyzing system inhibited diffusion of Fe NPs and facilitated the full reduction of Fe catalyst, thus facilitating the selective growth of SWNTs. DWNTs were also obtained by introducing a thick layer of Cu catalyst onto Fe/Al2O3. Our work provides a rational way for selective growth of vertically aligned SWNTs and DWNTs, whose remarkable e...

A sweet spot for highly efficient growth of vertically aligned single-walled carbon nanotube forests enabling their unique structures and properties.

We investigated the correlation between growth efficiency and structural parameters of single-walled carbon nanotube (SWCNT) forests and report the existence of a SWCNT "sweet spot" in the CNT diameter and spacing domain for highly efficient synthesis. Only within this region could SWCNTs be grown efficiently. Through the investigation of the growth rates for ∼340 CNT forests spanning diameters from 1.3 to 8.0 nm and average spacing from 5 to 80 nm, this "sweet spot" was found to exist because highly efficient growth was constrained by several mechanistic boundaries that either hindered the formation or reduced the growth rate of SWCNT forests. Specifically, with increased diameter SWCNTs transitioned to multiwalled CNTs (multiwall border), small diameter SWCNTs could only be grown at low growth rates (low efficiency border), sparse SWCNTs lacked the requirements to vertically align (lateral growth border), and high density catalysts could not be prepared (high catalyst density border). As a result, the SWCNTs synthesized within this "sweet spot" possessed a unique set of characteristics vital for the development applications, such as large diameter, long, aligned, defective, and high specific surface area.

Growth of high quality, high density single-walled carbon nanotube forests on copper foils

We demonstrate the growth of high quality single-walled carbon nanotube (SWCNT) forests on commercial Cu foils by cold-wall chemical vapor deposition. Time-of-flight secondary ion mass spectrometry was employed to study the effect of annealing on the catalyst evolution with or without an AlOx barrier layer. X-ray photoelectron spectroscopy was used to investigate the chemical states of the catalyst and the barrier layer. SWCNT forests can be reproducibly grown on Cu foils sputter-coated with Al and Fe layers as thin as 6 nm and 0.4 nm, respectively. Al transforms into AlOx on exposure to air and during annealing. Most importantly, such a thin AlOx barrier layer ensures not only the growth of SWCNTs but also an Ohmic contact between the as grown SWCNTs and the Cu base as measured by a two-point probe station. The as-grown SWCNTs exhibit a bimodal distribution of diameters ranging from 0.6 to 4.5 nm, with two peaks centered at 0.8 nn and 2.6 nm, respectively.

The Application of Gas Dwell Time Control for Rapid Single Wall Carbon Nanotube Forest Synthesis to Acetylene Feedstock.

One aspect of carbon nanotube (CNT) synthesis that remains an obstacle to realize industrial mass production is the growth efficiency. Many approaches have been reported to improve the efficiency, either by lengthening the catalyst lifetime or by increasing the growth rate. We investigated the applicability of dwell time and carbon flux control to optimize yield, growth rate, and catalyst lifetime of water-assisted chemical vapor deposition of single-walled carbon nanotube (SWCNT) forests using acetylene as a carbon feedstock. Our results show that although acetylene is a precursor to CNT synthesis and possesses a high reactivity, the SWCNT forest growth efficiency is highly sensitive to dwell time and carbon flux similar to ethylene. Through a systematic study spanning a wide range of dwell time and carbon flux levels, the relationship of the height, growth rate, and catalyst lifetime is found. Further, for the optimum conditions for 10 min growth, SWCNT forests with ~2500 μm height, ~350 μm/min initial growth rates and extended lifetimes could be achieved by increasing the dwell time to ~5 s, demonstrating the generality of dwell time control to highly reactive gases.

Nonlocal axial load-bearing capacity of two neighboring perpendicular single-walled carbon nanotubes accounting for shear deformation

This study is devoted to examine load-bearing capacity of a nanosystem composed of two adjacent perpendicular single-walled carbon nanotubes (SWCNTs) which are embedded in an elastic matrix. Accounting for the nonlocality and the intertube van der Waals forces, the governing equations are established based on the nonlocal Euler–Bernoulli, Timoshenko, and higher-order beam theories. These are sets of coupled integro-ordinary differential equations whose analytical solutions are unavailable. Hence, an efficient meshless methodology is proposed and the discrete governing equations are obtained via Galerkin approach. By solving the resulting set of eigenvalue equations, the axial buckling load of the elastically embedded nanosystem is evaluated. The roles of the radius and slenderness ratio of the constitutive SWCNTs, free distance between two tubes, small-scale parameter, aspect ratio, transverse and rotational stiffness of the surrounding matrix on the axial buckling load of the nanosystem are comprehensively addressed. The obtained results can be regarded as a pivotal step for better understanding the mechanism of elastic buckling of more complex systems such as elastically embedded-orthogonal membranes or even forests of SWCNTs.

Automated multiplexed ECL Immunoarrays for cancer biomarker proteins.

Point-of-care diagnostics based on multiplexed protein measurements face challenges of simple, automated, low-cost, and high-throughput operation with high sensitivity. Herein, we describe an automated, microprocessor-controlled microfluidic immunoarray for simultaneous multiplexed detection of small protein panels in complex samples. A microfluidic sample/reagent delivery cassette was coupled to a 30-microwell detection array to achieve sensitive detection of four prostate cancer biomarker proteins in serum. The proteins are prostate specific antigen (PSA), prostate specific membrane antigen (PSMA), platelet factor-4 (PF-4), and interlukin-6 (IL-6). The six channel system is driven by integrated micropumps controlled by an inexpensive programmable microprocessor. The reagent delivery cassette and detection array feature channels made by precision-cut 0.8 mm silicone gaskets. Single-wall carbon nanotube forests were grown in printed microwells on a pyrolytic graphite detection chip and decorated with capture antibodies. The detection chip is housed in a machined microfluidic chamber with a steel metal shim counter electrode and Ag/AgCl reference electrode for electrochemiluminescent (ECL) measurements. The preloaded sample/reagent cassette automatically delivers samples, wash buffers, and ECL RuBPY-silica-antibody detection nanoparticles sequentially. An onboard microcontroller controls micropumps and reagent flow to the detection chamber according to a preset program. Detection employs tripropylamine, a sacrificial reductant, while applying 0.95 V vs Ag/AgCl. Resulting ECL light was measured by a CCD camera. Ultralow detection limits of 10-100 fg mL(-1) were achieved in simultaneous detection of the four protein in 36 min assays. Results for the four proteins in prostate cancer patient serum gave excellent correlation with those from single-protein ELISA.

Synthesis of vertically aligned single-walled carbon nanotubes with metallic chirality through facet control of catalysts

For nanotube synthesis, iron platinum (FePt) alloy particles have been prepared on a single crystalline magnesium oxide (MgO) substrate by alternate sputter deposition of FePt and MgO. Partially facetted {111}-nano particles of FePt have been epitaxially formed on the substrate and periodically exposed on the surface. The particles of FePt were half-buried between deposited MgO showed superior thermal stability and microparticulations were also achieved by optimization of film layer thickness. By using the substrates for growth of carbon nanotubes, vertically aligned single-walled carbon nanotubes (forest) have been successfully grown on the substrate containing the faceted FePt nanoparticles. Raman spectra of the forest have revealed prominent features of metallic nanotubes in the radial breathing-mode region.

Wave characteristics in aligned forests of single-walled carbon nanotubes using nonlocal discrete and continuous theories

Elastic waves within forests of single-walled carbon nanotubes (SWCNTs) have been of particular interest to researchers of nanotechnology and applied physics. To date, wave motion in individual single-, double-, and multi- walled carbon nanotubes has been extensively investigated, however, characteristics of the transverse waves in three-dimensional clusters of SWCNTs have not been revealed. In this paper, using nonlocal Rayleigh, Timoshenko, and higher-order beam theories, shear and flexural frequencies as well as their corresponding phase and group velocities of transverse waves within such nanostructures are studied via discrete and continuous models. Using continuous models, the explicit expressions of the above-mentioned characteristics of waves are obtained. The efficacy of the proposed continuous models is proved by comparing their results with those of the nonlocal discrete models. The roles of wavenumber, radius of the constitutive SWCNTs, slenderness ratio, small-scale parameter, intertube distance, and population of the ensemble on the characteristics of transverse waves are comprehensively examined.

Strain engineering for thermal conductivity of single-walled carbon nanotube forests

We perform classical molecular dynamics simulations to investigate the mechanical compression effect on the thermal conductivity of the single-walled carbon nanotube (SWCNT) forest, in which SWCNTs are closely aligned and parallel with each other. We find that the thermal conductivity can be linearly enhanced by increasing compression before the buckling of SWCNT forests, but the thermal conductivity decreases quickly with further increasing compression after the forest is buckled. Our phonon mode analysis reveals that, before buckling, the smoothness of the inter-tube interface is maintained during compression, and the inter-tube van der Waals interaction is strengthened by the compression. Consequently, the twisting-like mode (good heat carrier) is well preserved and its group velocity is increased by increasing compression, resulting in the enhancement of the thermal conductivity. The buckling phenomenon changes the circular cross section of the SWCNT into ellipse, which causes effective roughness at the inter-tube interface for the twisting motion. As a result, in ellipse SWCNTs, the radial breathing mode (poor heat carrier) becomes the most favorable motion instead of the twisting-like mode and the group velocity of the twisting-like mode drops considerably, both of which lead to the quick decrease of the thermal conductivity with further increasing compression after buckling.

Dual-electrode measurements in a meniscus microcapillary electrochemical cell using a high aspect ratio carbon fibre ultramicroelectrode

The meniscus-based microcapillary electrochemical method (MCEM) allows electrochemical measurements to be made quickly and easily at a wide range of materials, simply by connecting up the sample of interest as a working electrode and bringing a capillary containing an electrolyte solution and quasi-reference/counter electrode into meniscus contact. In this work, microcapillary-based electrochemical methodology is advanced by introducing a very high aspect ratio carbon fibre ultramicroelectrode (CF-UME) allowing generation/collection and shielding (redox competition) measurements to be made. The experimental concept is demonstrated with the outer sphere (ferrocenylmethyl) trimethylammonium ion (FcTMA+/2+) redox mediator on a single walled carbon nanotube (SWNT) network. It is then used to investigate electrochemical reactions on a complex electrode, i.e. a SWNT forest, which is not easily investigated using traditional techniques that would require the electrode material to be physically encapsulated. The technique is most powerful when used to probe the different mechanistic pathways of the oxygen reduction reaction (ORR). This aspect is illustrated through studies on platinum, glassy carbon and SWNT forest electrodes. By platinising the CF-UME, the electrode can be used as a local sensor for the intermediate H2O2 and the O2 reactant, and it is possible to track the evolving consumption of these species near the working electrode during voltammetric measurements.

Diameter control of single-walled carbon nanotube forests from 1.3–3.0 nm by arc plasma deposition

We present a method to both precisely and continuously control the average diameter of single-walled carbon nanotubes in a forest ranging from 1.3 to 3.0 nm with ~1 Å resolution. The diameter control of the forest was achieved through tuning of the catalyst state (size, density, and composition) using arc plasma deposition of nanoparticles. This 1.7 nm control range and 1 Å precision exceed the highest reports to date.

Observation of localized strains on vertically grown single-walled carbon nanotube forests via polarized Raman spectroscopy

Vertically grown single-walled carbon nanotube (V-SWCNT) forests, synthesized by water-assisted plasma-enhanced chemical vapor deposition, were studied using polarized micro-Raman spectroscopy. Among three different sections (root, center and end) along the vertical growth direction, the degree of V-SWCNT alignment was highest in the center section. Raman frequency red-shifts up to 7 and 13 cm−1, for RBM and G-band, respectively, were observed in the center section, with respect to the Raman frequencies measured in the root and the end sections. Raman frequency downshift and concurrent linewidth broadening of the G-band, revealing a localized strain, were also observed in the center section. The existence of a localized strain in the center section of the V-SWCNT was further confirmed by observing a strong polarization anisotropy of up to 8 cm−1 in the G-band Raman frequency for different polarized Raman scattering configurations at the same probed spot.

Influence of lengths of millimeter-scale single-walled carbon nanotube on electrical and mechanical properties of buckypaper

The electrical conductivity and mechanical strength of carbon nanotube (CNT) buckypaper comprised of millimeter-scale long single-walled CNT (SWCNT) was markedly improved by the use of longer SWCNTs. A series of buckypapers, fabricated from SWCNT forests of varying heights (350, 700, 1,500 μm), showed that both the electrical conductivity (19 to 45 S/cm) and tensile strength (27 to 52 MPa) doubled. These improvements were due to improved transfer of electron and load through a reduced number of junctions for longer SWCNTs. Interestingly, no effects of forest height on the thermal diffusivity of SWCNT buckypapers were observed. Further, these findings provide evidence that the actual SWCNT length in forests is similar to the height.

Absence of an Ideal Single-Walled Carbon Nanotube Forest Structure for Thermal and Electrical Conductivities

We report the fundamental dependence of thermal diffusivity and electrical conductance on the diameter and defect level for vertically aligned single-walled carbon nanotube (SWCNT) forests. By synthesizing a series of SWCNT forests with continuous control of the diameter and defect level over a wide range while holding all other structures fixed, we found an inverse and mutually exclusive relationship between the thermal diffusivity and the electrical conductance. This relationship was explained by the differences in the fundamental mechanisms governing each property and the optimum required structures. We concluded that high thermal diffusivity and electrical conductance would be extremely difficult to simultaneously achieve by a single SWCNT forest structure within current chemical vapor deposition synthetic technology, and the "ideal" SWCNT forest structure would differ depending on application.

A Fundamental Limitation of Small Diameter Single-Walled Carbon Nanotube Synthesis-A Scaling Rule of the Carbon Nanotube Yield with Catalyst Volume.

Understanding the fundamental mechanisms and limiting processes of the growth of single-walled carbon nanotube (SWCNT) would serve as a guide to achieve further control on structural parameters of SWCNT. In this paper, we have studied the growth kinetics of a series of SWCNT forests continuously spanning a wide range of diameters (1.9–3.2 nm), and have revealed an additional fundamental growth limiting process where the mass of the individual SWCNT is determined by the individual catalyst volume. Calculation of the conversion rate of carbon atoms into CNTs per Fe atom is 2 × 102 atoms per second. This rate limiting process provides an important understanding where the larger diameter SWCNT would grow faster, and thus be more suited for mass production.

Diameter and Density Control of Single‐Walled Carbon Nanotube Forests by Modulating Ostwald Ripening through Decoupling the Catalyst Formation and Growth Processes

A continuous and wide range control of the diameter (1.9-3.2 nm) and density (0.03-0.11 g cm(-3) ) of single-walled carbon nanotube (SWNT) forests is demonstrated by decoupling the catalyst formation and SWNT growth processes. Specifically, by managing the catalyst formation temperature and H2 exposure, the redistribution of the Fe catalyst thin film into nanoparticles is controlled while a fixed growth condition preserved the growth yield. The diameter and density are inversely correlated, where low/high density forests would consist of large/small diameter SWNTs, which is proposed as a general rule for the structural control of SWNT forests. The catalyst formation process is modeled by considering the competing processes, Ostwald ripening, and subsurface diffusion, where the dominant mechanism is found to be Ostwald ripening. Specifically, H2 exposure increases catalyst surface energy and decreases diameter, while increased temperature leads to increased diffusion on the surface and an increase in diameter.

Enhancement of heterogeneous electron transfer dynamics tuning single-walled carbon nanotube forest height and density

Electrochemical sensors are growing in number and importance. Surface modifications could enhance charge transfer properties occurring at the interfaces and carbon nanoassemblies is one of the most used strategy to improve sensitivity to measurements. However, well defined protocols of surface modification are needed in order to fabricate electrochemically effective nanostructured sensors.Therefore, we aim at investigating the electrochemical properties of single-walled carbon nanotube (SWCNT) forests as a function of height and nanotube surface density. Height of the forests is accurately controlled tuning the oxidation temperatures in the range of 293–313K of SWCNTs. The surface density of carbon nanotubes was adjusted developing cysteamine/2-mercaptoethanol (CYS/ME) self-assembled monolayers (SAMs) on gold surfaces at different ratios (1:0, 1:3, 1:10, 1:100, 0:1).Apparent electron transfer rate was analyzed with electrochemical impedance spectroscopy (EIS) and experimental data show that transfer rate constant, kapp, increases from 1×10−4cm/s to 6×10−4cm/s rising oxidation temperatures (i.e. lowering forest height); therefore forests with reduced height show higher electron transfer rate without significant difference in electrodic reversibility. On the other hand, tuning SWCNT surface density, forests obtained with no ME show optimal Δpeak value of 0.087±0.015V and highest kapp value of 9.15×10−3cm/s. Surprisingly, electrochemical surface area analysis shows that samples with lower amount of cysteamine have an active surface area three times bigger than samples with 1:3 CYS/ME ratio. Low electrochemical efficiency associated with high active surface may be related to unwanted SWCNT bundles adsorbed on the surface for 1:10 and 1:100 CYS/ME ratio samples as confirmed by AFM morphological characterization. Further investigation shows that a transition from a semi-infinite planar diffusion mechanism to a radial diffusion one takes place when SAMs with low chemical affinity to nanotubes are used. Wettability analysis confirms the robustness of the surface chemical modification during the forest development. Altogether these results show that optimal electrochemical properties of carbon modified electrodes require an accurate control of forest fabrication in terms of carbon nanotube structural assembling.