Modulating electronic transport properties of carbon nanotubes to improve the thermoelectric power factor via nanoparticle decoration.

Nanoparticle decoration on carbon nanotubes was employed to modulate their electrical conductance and thermopower and thereby improved the thermoelectric power factor. Nanotubes were made into films by spraying nanotube solutions on glass substrates, and then the films were immersed in different concentrations of CuSO(4) or HAuCl(4) solutions for various time periods. Copper ions in the solutions were reduced on nanotubes by obtaining electrons from zinc electrodes, whose reduction potential is lower than that of copper (galvanic displacement). Gold ions were reduced on nanotubes by both silver counter electrodes and spontaneous reaction due to larger reduction potentials than those of nanotubes. These reactions made electrons donated to (copper incorporation) or withdrawn from (gold incorporation) nanotubes depending on the difference in their work functions and reduction potentials, resulting in considerable changes in electron transport. In this paper, a series of experiments at different ion concentrations and reaction time periods were systematically performed in order to find optimum nanoparticle formation conditions and corresponding electronic transport changes for better thermoelectric power factor. Transport measurement results show that electronic properties can be considerably altered and modulated, resulting in 2-fold improvement in the thermoelectric power factor with 1 mM/30 min reaction. Reactions with solutions of a low metal ion concentration, such as 1 mM, yielded well-distributed small particles over large surface areas, which strongly affected electron transfer between nanoparticles and nanotubes. Successive copper and gold decorations on nanotubes made electrical conductance (or thermopower) serially decreased and increased (or increased and decreased) upon precipitating different metal particles. This transport behavior is believed to be from the changes in the Fermi level as a result of electron exchanges between reduced metals and nanotubes. Thermopower improvement after copper decoration can be attributed to the enlarged gap between the Fermi level and the mean of differential electrical conductivity. Such behaviors often appear when the Fermi level is shifted toward the spike-shape density of states in nanotubes due to anisotropic differential electrical conductivity. Finally, this study demonstrates that the thermoelectric power factor can be considerably increased by properly locating the Fermi level of carbon nanotubes with nanoparticles, providing promising opportunities of developing efficient organic thermoelectric materials as well as various electronic materials of desired properties.