AVS1999 Session NT+NS+EM+MS-ThA: Nanotubes: Functionalization and Metrology

Thursday, October 28, 1999 2:00 PM in Room 6C

Thursday Afternoon

Start	Invited?	Item
2:00 PM	Invited	NT+NS+EM+MS-ThA-1 Opportunities and Challenges for Nanotubes in Future Integrated Circuits R.R. Doering (Texas Instruments) We speculate about a few potential research opportunities that may be of mutual interest to both the microelectronics and nanotube communities. Perhaps the most evolutionary use of nanotubes in integrated circuits would be in the form of "thin films." Such use would capitalize on "bulk" material properties. For example, a layer of nanotubes (with "best metallic" conductivity) might serve as an interconnect film. Alternatively, an insulating nanotube layer (e.g, "modified" CNTs or other tube chemistries) might be used as a low-K dielectric. Even lower K might be achieved by using high-conductivity CNTs as "self-supporting wires," taking advantage of their inherent mechanical strength to eliminate the need for solid insulating layers. Another type of evolutionary use might involve nanotube structures for passive IC components. For example, the huge volume density of surface area looks appealing for DRAM capacitors. A significant amount of current nanotube research is aimed at active devices, which might ultimately replace today's silicon semiconductor switches. One of the most exciting prospects is the potential for more extensive and effective use of the "third-dimension" in integrated circuits. However, as with today's "planar" IC technology, the benefit/cost of "going 3D" will depend on details of the practical fabrication techniques. For nanotubes, this brings up "formation/place/route" issues. Nanotubes may also play a role in future "atomically perfect manufacturing," which may be needed to scale much below about 50-nm features regardless of the type of device technology employed.
3:00 PM		NT+NS+EM+MS-ThA-4 Simulations of Plasticity and Kink Catalyzed Functionalization of C and BN Nanotubes D. Srivastava (NASA Ames Research Center); M. Menon (University of Kentucky) Routes to plasticity and kink catalyzed chemistry for functinlaization of C and BN nanotubes are investigated via classical molecular dynamics (MD) and generalized tight-bonding quantum molecular dynamics (QMD) methods. The critical strain for plasticity of BN nanotube is found to be more than that for the similar C nanotube. The structural collapse of nanotubes under compression is explored in which we find that the accumulated strain drives the tube in a plastic deformation in which four-fold coordinated tetrahedral bonds form at the location of the collapse. This lowers the elastic limit of compressed nanotubes to much less than what was predicted earlier with classical MD potential methods alone.¹ The critical stress needed for this transition, as computed with QMD method, is in good agreement with experimental values observed for compressed nanotubes in polymer composites and graphite to diamond like transition in a bucky-onion pressure cell. Mechanical kink driven side-wall functionalization of C and BN nanotubes is also explored. We find that mechanical twisting and bending of the tube enhances the binding energy (and lowers the cohesive energy) at kink or edge sites by 1-2 eV as compared to the reactivity of undeformed tubes. Highly localized selective functionalization and etching of sidewalls could thus be possible through kink catalyzed chemical reactivity of nanotubes. A preliminary example of the experimental evidence will be shown.² ¹D. Srivastava, M. Menon, and K. Cho, submitted (1999). ²D. Srivastava, D. W. Brenner, J. D. Schall, K. D. Ausman, M. F. Yu and R. S. Ruoff, to appear J. Phys. Chem. (1999).
3:20 PM		NT+NS+EM+MS-ThA-5 Nanoindentation and Nanotribology with Carbon Nanotubes B. Ni, A. Garg, S.B. Sinnott (University of Kentucky) The mechanisms by which carbon nanotubule (CNT) proximal probe tips deform during the nanometer-scale indentation and scratching of surfaces are explored using classical molecular dynamics simulations. The forces acting on the atoms in the simulations are calculated using a many-body, reactive bond-order potential for hydrocarbons. The results show that single-walled and multiwalled CNT tips indented against hydrogen-terminated diamond and graphene surfaces buckle and slip to relieve the applied stress. However, in the case of reactive surfaces, tip-surface adhesion occurs on contact that ultimately destroys the tubule. Furthermore, while shell-shell interactions have little effect on the deformation mechanisms, the multiwalled tubule is stiffer than comparably sized single-walled tubules. Finally, the way in which the deformation of these tubules changes during scratching of diamond and graphene surfaces will be discussed and the results compared to available experimental data. Supported by NASA Ames Research Center (NAG 2-1121) and NSF MRSEC (DMR-9809686).
3:40 PM		NT+NS+EM+MS-ThA-6 Quantum Chemistry Study of Carbon Nanotube Fluorination R.L. Jaffe (NASA Ames Research Center) Quantum chemistry calculations are carried out to characterize the products of fluorination reactions of C₆₀, C₇₀ and carbon nanotubes. The calculations utilize density functional theory with a widely used hybrid nonlocal functional (B3LYP-DFT). C₆₀ is known to readily undergo reaction with molecular fluorine to form C₆₀F_n with n<44. C₆₀F₁₈ and C₆₀F₃₆ are the predominate products. C₇₀ also is known to undergo similar reaction, but the products have not been completely characterized. Less is known about the possibility of fluorinating nanotubes. However, it has been conjectured that highly fluorinated nanotubes may have attractive chemical and dielectric properties. Fluorination of C₆₀ and C₇₀ is used to benchmark the calculations for nanotubes. Previous studies have demonstrated that polycyclic aromatic hydrocarbons with an externally constrained curvature are good model molecules for studying the functionalization reactions of single-walled carbon nanotubes. Reaction is likely if the products are energetically stable and any activation energy barriers are small. Initial studies for C₆₀ and (10,10) nanotubes have shown that the difluoronated products are quite stable and the fluorination reaction is highly exothermic.
4:00 PM		NT+NS+EM+MS-ThA-7 Gear-like Rolling Motion of Carbon Nanotubes on HOPG M.R. Falvo, J. Steele, A. Buldum (University of North Carolina, Chapel Hill); D. Schall (North Carolina State University); R.M. Taylor II (University of North Carolina, Chapel Hill); D.W. Brenner (North Carolina State University); J. Lu, R. Superfine (University of North Carolina, Chapel Hill) Though much work has been done in recent years in exploring nanometer and atomic scale sliding friction, little experimental or theoretical work has been done on rolling and its relation to sliding at this scale. We will present lateral force microscope investigations of frictional phenomena of multiwall carbon nanotubes (MWCNTs) on highly oriented pyrolytic graphite (HOPG), that include all the rigid body motions: sliding, rotating in-plane, and rolling. Using an advanced manipulation interface for AFMs, the nanoManipulator, we study these friction phenomena through sophisticated manipulation experiments where lateral forces are monitored during manipulations. We have manipulated MWCNTs into a state of atomic registry between the lattice of the tube and underlying substrate. Out of atomic registry the friction is smooth and uniform. As the CNT is rotated in the plane of the substrate, three discrete atomically registered orientations are observed marked by a 3-10 fold increase in the lateral force required to remove them from these orientations. Results of molecular statics calculations for this system show that the potential energy as a function of in-plane rotation angle has three deep minima spaced sixty degrees apart corresponding to atomic lattice registry. When the CNT locks into atomic registry, there is a transition from an in-plane rotational motion to a stick-slip rolling motion. Rather than being perfectly cylindrical, our lateral force data during rolling indicate that the CNT may be faceted (polygonal cross section). MS calculations indicate that faceting is to be expected for MWCNT depending on diameter and wall thickness. The calculated friction expected for rolling a faceted MWCNT agrees well with experimental lateral force data. Molecular dynamics calculations will be shown that lend insight into the energy loss mechanisms for both the sliding and rolling case. This work is supported by the NIH (NCRR), NSF, ONR (MURI), and ARO (DURIP).
4:20 PM		NT+NS+EM+MS-ThA-8 Selectivity and Diffusion of Binary Fluids in Carbon Nanotubes Z. Mao, S.B. Sinnott (University of Kentucky) Carbon nanotube bundles have been proposed as good materials for the manufacture of tailored ultrafiltration membranes due to their uniform, porous structure. In contrast to conventional membranes produced by only partially sintering a ceramic or stretching a polymer, a nanotube membrane would offer the advantages of fewer blocked pores and a narrower distribution of pore sizes. To investigate the properties of a nanotube membrane, the adsorption of simple binary fluids within single tubules and tubule bundles are modeled using atomistic simulations. Specifically, classical molecular dynamics simulations are performed using a combined many-body, reactive bond-order and Lennard-Jones potential. The results show how the diffusion of these molecules proceeds at differing rates within the nanotubes as a function of the diameter and helical structure of the tubules, the density of the fluid, the size difference between the molecules, and temperature. An example of a binary fluid that has been studied is a mixture of CH₄ and C₄H₁₀ at room temperature. The simulations predict high selectivity in the diffusion of these molecules through the nanotubes. They also allow for the determination of the type of diffusion followed by each type of fluid molecule. Comparisons will be made between these simulation results and the results of similar studies in the literature of diffusion in zeolites and other molecular sieves. Supported by NASA Ames Research Center (NAG 2-1121) and NSF MRSEC (DMR-9809686).
4:40 PM		NT+NS+EM+MS-ThA-9 Improved Tungsten Disulfide Nanotubes as Tips for Scanning Probe Microscopy A. Rothschild, G. Frey, M. Homyonfer, M. Rappaport, S.R. Cohen, R. Tenne (Weizmann Institute of Science, Israel) Synthesis and applications of long and hollow WS₂ nanotubes are described. Although synthesis of nanotubes from various inorganic compounds have been reported, the high yields of uncontaminated nanotubes reported here represents a significant improvement over past efforts by ourselves and others.¹,² The nanotubes are synthesized in a two-step process the first being the creation of WO₃ nanoparticles by heating a tungsten filament in the controlled presence of water. The second step, sulfidization, resulted in a 30 times increase in the length of these particles without change in width so that nanotubes up to 10 microns in length and 20-40 nm width were formed. These tubes were attached to scanning force microscope (SFM) tips and used to image deep and sharp features inaccessible by sharp silicon tips. Due to their sandwich S-W-S structure, these nanotubes are probably stiffer than the carbon analogs and hence less prone to instabilities under such rigorous scanning conditions. We propose application of these probes for nanophotolithography, aided by the facile excitation of these compounds by visible and infra-red light. Support by the Israel Ministry of Science, Israel Science Foundation, and Applied Materials-Weizmann Foundation are gratefully acknowledged. A.R. is a recipient of the Lavoisier fellowship (France). ¹ Y. Feldman, E. Wasserman, D.J. Srolovitz, R. Tenne, Science 267, 222 (1995). ² N.G. Chopra, et al, Science 269, 966 (1995).