Persistence Length Control of the Polyelectrolyte Layer-by-Layer Self-Assembly on Carbon Nanotubes

One-dimensional inorganic materials such as carbon nanotubes1 and semiconductor nanowires have been central to important advances in materials science in the last decade. Unique mechanical and electronic properties of these molecular-scale wires enabled a variety of applications ranging from novel composite materials, to electronic circuits, to new sensors. Often, these applications require non-covalent modification of carbon nanotubes with organic compounds, DNA and biomolecules, and polymers to change nanotube properties or to add new functionality. We recently demonstrated a versatile and flexible strategy for non-covalent modification of carbon nanotubes using layer-by-layer self-assembly of polyelectrolytes. Researchers used this technique extensively for modification of flat surfaces, micro-, and nano-particles; however, little is known about the mechanism and the factors influencing layer-by-layer self-assembly in one-dimensional nanostructures. The exact conformation of polyelectrolyte chains deposited on single-walled carbon nanotubes (SWNT) is still unknown. There are two possible configurations: flexible polymers wrapping around the nanotube and stretched, rigid chains stacked parallel to the nanotube axis. Several factors, such as polymer rigidity, surface curvature, and strength of polymer-surface interactions, can determine the nature of assembly. Persistence length of the polymer chain should be one of the critical parameters, since it determines the chain's ability to wrap around the nanotube. Indeed, computer simulations for spherical substrates show that polymer rigidity and substrate surface curvature can influence the deposition process. Computational models also show that the persistence length of the polymer must fall below the threshold values determined by target surface curvature in order to initiate polyelectrolyte deposition process. Although these models described the effects of salt concentration and target surface curvature, they considered only nano-particles with radius 5 nanometer and larger. One-dimensional materials, such as carbon nanotubes, provide an even more interesting template for studying self-assembly mechanisms, since they give us access to even smaller surface curvatures down to 1 nm. We have examined the role of the polymer persistence length in layer-by-layer self-assembly process on carbon nanotubes by observing formation of multilayer polyelectrolyte shells around carbon nanotubes at different ionic strength. Persistence length of polyelectrolytes varies with solution ionic strength, due to screening of the electrostatic repulsion between the polymer Figure 1. TEM images of single-walled carbon nanotubes after polymer deposition for ionic strengths of (A) 0.05M, (B) 0.1M, (C) 0.2M, (D) 0.4M, (E) 0.65M, and (F) 1.05M. Scale bar corresponds to 10 nm. backbone charges; therefore changing ionic strength is a convenient way to alter the configuration of the polymer molecule systematically. We have used the layer-by-layer self-assembly technique to form 5-layer thick coating of the alternating polyallylamine hydrochloride (PAH) and sodium poly(styrenesulfonate) (PSS) layers on the surfaces of the pristine single-wall carbon nanotubes. For our experiments, we grew the nanotubes across copper TEM grid openings using catalytic chemical vapor deposition. The deposition solutions contained different amounts of NaCl to vary the ionic strength. After polymer multilayer formation we examined the resulting coating in high-resolution TEM