Session A27: Carbon Nanotube & Related Materials: Growth, Separation, and Assembly

Nonequilibrium statistical mechanics of nanotube nucleation

A key problem that advanced carbon nanotube applications face is the difficulty of producing pure single-helicity samples. As the elementary processes of nanotube growth are difficult to observe in situ, theoretical understanding of the process is especially important. Direct molecular dynamics simulations offer limited insight due to computational intractability of space- and time-scales involved. We formulated a theory that explains a class of helicity-selective growth experiments, based on classical nucleation theory and crystal growth kinetics.$^{\mathrm{1}}$ However, a general theory of nanotube growth must also include fast irreversible growth beyond the classical near-equilibrium assumption. Here we construct a coarse-grained model allowing us to rigorously investigate the statistical mechanics of nanotube nucleation and trace how helicity emerges from the global nucleation trajectory ensemble. Importantly, our model can handle the whole range of conditions from perfect reversibility driven by energetics to perfect irreversibility driven by configurational entropy of nanotube caps and edges. Our theory generalizes earlier models in a large advance towards ultimate understanding of helicity-selective synthesis. $^{\mathrm{1}}$ V.I. Artyukhov, E.S. Penev, and B.I. Yakobson, Nat. Commun. 5, 4892 (2014)   

Adsorption of SDS surfactant inside and around carbon nanotubes with DPD simulation

The inner diameter of a carbon nanotube (CNT) is generally from 1 to 20 nm, while its inner space could be filled by certain compounds. In our study, Dissipative Particle Dynamics (DPD) simulations were utilized to investigate the ability of sodium dodecyl sulfate (SDS) to adsorb inside a single-walled CNT. First of all, the DPD interaction parameters for SDS surfactants were validated by determining the CMC of surfactants from DPD calculation. The SDS micelle shape and size in water were also calculated. Water-CNT interactions were obtained from a prior study [1]. When the SDS aqueous system reached equilibrium, an open-ended, hydrophobic CNT (a hollow cylinder in the simulation) was inserted into the solution. The diameter of the CNT varied from 1 to 5 nm. All simulations were run up to 2x10$^{\mathrm{6}}$ time steps at room temperature. For the system of water and CNT, the radial and axial density profiles of water were computed and compared with published Molecular Dynamics results. In the presence of SDS, the distribution of water and SDS inside the CNT was found to be comparable to that in bulk solution after the system reached equilibrium. In addition, the diffusivity and residence time of water and SDS inside CNTs of different were calculated. This study would give insights into the dynamics and morphology of surfactants in nanoconfined structures. References [1] Vo, M.; Papavassiliou, D. V., Molecular Simulation, 2015, DOI:10.1080/08927022.2015.1089989   

Intensity Ratio of Resonant Raman Modes for ($n,m)$ Enriched Semiconducting Carbon Nanotubes

Relative intensities of resonant Raman spectral features, specifically the radial breathing mode (RBM) and G modes, of eleven, chirality-enriched, single-wall carbon nanotube (SWCNT) species were established under second-order optical transition excitation. The results demonstrate a significantly under-recognized complexity in the evaluation of Raman spectra for the assignment of ($n,m)$ population distributions. Strong chiral angle and mod dependencies affect the intensity ratio of the RBM to G modes and can result in misleading interpretations. Furthermore, we report five additional values for chirality dependent G$^{+}$ and G$^{-}$ Raman peak positions and intensities, supporting accuracy in literature values, and extending the available data to cover more of the small diameter regime by including the first (5,4) second-order, resonance Raman spectra. Together, the Raman spectral library is demonstrated to be sufficient for decoupling multiple species via a spectral fitting process, and enable fundamental characterization even in mixed chiral population samples.   

Structure-Controlled Synthesis of Single-Walled Carbon Nanotubes

Single-walled carbon nanotubes (SWNTs) present structure-determined outstanding properties and SWNTs with a single (n, m) type are needed in many advanced applications. However, the chirality-specific growth of SWNTs is always a great challenge. Carbon nanotubes and their caps or catalysts can all act as the structural templates to guide the formation of SWNTs with a specified chirality. SWNT growth via a catalyzed chemical vapor deposition CVD process is normally more efficient and therefore of great interest. We developed a new family of catalyst, tungsten-based intermetallic nanocrystals, to grow SWNTs with specified chiral structures. Such intermetallic nanocrystals present unique structure and atomic arrangements, which are distinctly different from the normal alloy nanoparticles or simple metal nanocrystals, therefore can act as the template to grow SWNTs with designed (n, m) structures. Using W6Co7 catalysts, we realized the selective growth of (12, 6), (16, 0), (14, 4) and other chiralities. By the cooperation of thermodynamic and kinetic factors, SWNTs with high chirality purity can be obtained. .   

Growth of Single-Walled Carbon Nanotubes by High Melting Point Metal Oxide Catalysts

We report on the growth of single-walled carbon nanotubes (SWNTs) from Co oxide catalysts. The concept is using the relatively lower mobility of metal oxide (than metal) to suppress catalyst aggregation at high temperatures. Compared to the SWNTs grown by pre-reduced catalysts, SWNTs grown from oxidized Co catalysts have shown narrower diameter distribution and smaller average diameter. Different growth parameters are discussed regarding the resulting morphology of SWNTs. Transmission electron microscopy (TEM) investigations reveal the information that Co catalysts are transformed to Co3O4 after reduction-calcination process. X-ray photoelectron spectroscopy (XPS) investigations indicate that Co3O4 has decomposed to CoO before growth at a typical growth temperature (800 ºC) in Ar atmosphere. We propose that CoO has higher melting point than Co and thus is more stable during the growth. Our results indicate that besides the bimetallic catalysts, monometallic catalytic system could also be useful in stabilizing the catalysts to grow chirality-specific SWNTs by transforming the relatively low melting point metal catalysts to high melting point metal oxide catalysts.   

Endohedral Volume Control for Improved Single-Wall Carbon Nanotubes

Liquid-phase processing of single-wall carbon nanotubes (SWCNTs) generally results in the exposure of their core volumes to the environment (opening) due to energy input necessary for purification and solubilization. For aqueous processing this results in SWCNTs routinely getting filled with water, which is detrimental to several properties. Importantly, water filling leads to significant redshifts to, and inhomogeneous broadening of, the electronic transitions of the SWCNTs, as well as a substantial decrease to their fluorescence quantum efficiency. Selection of (remaining) empty (end-capped) SWCNTs to avoid these adverse effects is possible by means of ultracentrifugation, but is a natively low yield process. In this work, SWCNTs are prefilled with linear alkanes or similar organic compounds, serving as a passive, highly homogeneous spacer, blocking the ingestion of water and hence preventing the detrimental consequences. Moreover, the low dielectric nature of the alkane core only weakly affects the local electronic wavefunction of the SWCNTs, effectively simulating empty core conditions and hence yielding much more resolved optical spectra with blue shifted peak positions compared to water filled SWCNTs. It is demonstrated that a wide variety of linear as well as cyclic alkanes can be applied for this purpose, in combination with various SWCNT materials.   

Optical excitation of carbon nanotubes drives stoichiometric reaction with diazonium salts

Covalent chemistry is known to lack the precision required to tailor the physical properties of carbon nanostructures. Here we show that, for the first time, light can be used to drive a typically inefficient reaction with single-walled carbon nanotubes in a more stoichiometric fashion. Specifically, our experimental results suggest that light can enhance the reaction rate of diazonium salt with carbon nanotubes by as much as 35-fold, making possible stoichiometric control of the covalent bonding of a functional group to the sp$^{2}$ carbon lattice. This light-controlled reaction paves the way for the possibility of highly selective and precise chemistry on single-walled carbon nanotubes and other graphitic nanostructures.   

Chirality-controlled synthesis and macro-electronic applications of carbon nanotubes

Carbon nanotubes (CNTs) are promising materials for electronic applications due to their interesting properties. Chirality and electronic property controlled preparation are key challenges which need to be solved for practical use of CNTs in electronics. In this talk, I will first introduce our research on chirality-controlled synthesis of CNTs using metal-free carbon seeds. I will talk about chirality-controlled growth of SWCNTs using chirality-sorted nanotube seeds via a vapour phase epitaxy (VPE) cloning approach. Observations on the chirality-dependent growth rate and active lifetime of the nanotube seeds in the VPE process will be presented. Later, I will talk about selective growth of small diameter semiconducting CNTs using organic chemistry synthesized molecular seeds. In the second part, I will talk about the use of pre-separated, semiconducting-enriched CNTs for macro-electronics, printed electronics, and integrated circuits. Our work on the use of CNTs for thin-film transistors, CNT-IGZO hybrid CMOS circuits, and flexible, bendable, and transparent CNT devices and circuits will be presented. These works demonstrate the great potential of CNTs as advanced electronic materials.   

Uniformly spaced arrays of purely semiconducting carbon nanotubes

Patterning uniformly spaced arrays of carbon nanotubes (CNTs) is a key challenge for carbon electronics. Our group adopts a hybrid approach to meeting this goal. We use top-down lithography to pattern trenches on chips. We then use surface-selective chemical monolayers to facilitate the bottom-up assembly of solution-processed CNTs into these trenches. Previously, we showed large-scale integration of CNTs based on this approach [1], but modifications to this process have been needed in order to improve the yield and decrease the fraction of non-switching devices. Our latest results show a high degree of selectivity, alignment and yield of successfully placed CNTs at a 100 nm pitch. Electrical measurements confirm that these chemically placed CNTs are nearly 100{\%} semiconducting and of similar quality to randomly dispersed ones. I will then discuss our strategies for increasing the CNT density and extending these results from chip- to wafer-scale electronics. [1] Park et al., Nature Nanotechnology 7, 787-791 (2012)   

Nanoscale Structure and Interaction of Compact Assemblies of Carbon Nano-Materials.

Carbon-based nano-materials (CNM) are a diverse family of multi-functional materials under research and development world wide. Our work is further motivated by the predictive power of the physical understanding of the underlying structure-interaction-function relationships. Here we present results form recent studies of the condensed phases of several model CNMs in complexation with biologically derived molecules. Specifically, we employ X-ray diffraction (XRD) to determine nanoscale structures and use the osmotic stress method to quantify their interactions. The systems under investigation are dsDNA-dispersed carbon nanotubes (dsDNA-CNT), bile-salt-dispersed carbon nanotubes, and surfactant-assisted assemblies of graphene oxides. We found that salt and molecular crowding are both effective in condensing CNMs but the resultant structures show disparate phase behaviors. The molecular interactions driving the condensation/assembly sensitively depend on the nature of CNM complex surface chemistry and range from hydrophobic to electrostatic to entropic forces.   

Synthesis and Investigation of Millimeter-Scale Vertically Aligned Boron Nitride Nanotube Arrays

Boron nitride nanotubes (BNNTs) have shown potential in a wide range of applications due to their superior properties such as exceptionally high mechanical strength, excellent chemical and thermal stabilities. However, previously reported methods to date only produced BNNTs with limited length/density and insufficient yield at high temperatures. Here we present a facile and effective two-step synthesis route involving template-assisted chemical vapor deposition at a relatively low temperature of 900 degree C and subsequent annealing process to fabricate vertically aligned (VA) BN coated carbon nanotube (VA-BN/CNT) and VA-BNNT arrays. By using this method, we achieve the longest VA-BN/CNTs and VA-BNNTs to date with lengths of over millimeters (exceeding two orders of magnitude longer than the previously reported length of VA-BNNTs). In addition, the morphology, chemical composition and microstructure of the resulting products, as well as the mechanism of coating process are systematically investigated. This versatile BN coating technique and the synthesis of millimeter-scale BN/CNT and BNNT arrays pave a way for new applications especially where the aligned geometry of the NTs is essential such as for field-emission, interconnects and thermal management.