High resolution far infrared absorption measurements were carried out for single walled and double walled carbon nanotubes samples (SWCNT and DWCNT) encased in a polyethylene matrix to investigate the temperature and bundling effects on the low frequency phonons associated with the low frequency circumferential vibrations. At a temperature where kBT is significantly lower than the phonon energy, the broad absorption features as observed at room temperature become well resolved phonon transitions. For a DWCNT sample whose inner tubes have a similar diameter distribution as the SWCNT sample studied, a series of sharp features were observed at room temperature at similar positions as for the SWCNT samples studied. The narrow linewidth is attributed to the fact that the inner tubes are isolated from the polyethylene matrix and the weak inter-tubule interactions. More systematic studies will be required to better understand the effects of inhomogeneous broadening and thermal-excitation on the detailed position and lineshape of the low frequency phonon features in carbon nanotubes.

The concept of using nanocomposite thermoelectric materials in bulk form for practical applications is presented. Laboratory studies have shown the possibilities of nanostructures to yield large reductions in the thermal conductivity while at the same time increasing the power factor. Theoretical studies have suggested that structural ordering in nano-systems is not necessary for the enhancement of ZT, leading to the idea of using nanocomposites as a practical scale-up technology for making bulk thermoelectric materials with enhanced ZT values. Specific examples are presented of nanocomposite thermoelectric materials developed by our group based on the familiar silicon germanium system, showing enhanced thermoelectric performance through nano-structuring.

Extended abstract of a paper presented at Microscopy and Microanalysis 2006 in Chicago, Illinois, USA, July 30 – August 3, 2006

Extended abstract of a paper presented at Microscopy and Microanalysis 2005 in Honolulu, Hawaii, USA, July 31--August 4, 2005

The following article is based on the plenary presentation given by Mildred S. Dresselhaus of the Massachusetts Institute of Technology on November 29, 2004, at the Materials Research Society Fall Meeting in Boston. Advanced materials offer new promise for addressing some of the grand societal challenges of our future, including that of global energy. This article will review opportunities that have opened up at the nanoscale, with materials of reduced dimensionality and enhanced surface-to-volume ratio. Some examples of research accomplishments and opportunities at the nanoscale will be described, with special attention given to the potential for advanced materials and nanoscience to have an impact on the grand challenges related to a sustainable energy supply for the 21st century and beyond.

Many of the recent advances in enhancing the thermoelectric figure of merit are linked to nanoscale phenomena with both bulk samples containing nanoscale constituents and nanoscale materials exhibiting enhanced thermoelectric performance in their own right. Prior theoretical and experimental proof of principle studies on isolated quantum well and quantum wire samples have now evolved into studies on bulk samples containing nanostructured constituents. In this review, nanostructural composites are shown to exhibit nanostructures and properties that show promise for thermoelectric applications. A review of some of the results obtained to date are presented.

In this paper we report the effects of strain on the electronic properties of single wall carbon nanotubes and its consequence on the resonant Raman cross section. A quantum interference effect has been predicted for the radial breathing mode spectra for metallic tubes. For metallic tubes, the lower and upper components of Eii resulting from the trigonal warping effect are affected differently and for low chiral angle they cross for some strain value. Near (at) the crossing point, the resonant Raman spectra profile exhibits a maximum (minimum) value due to a quantum interference in the Raman cross section. This Raman cross section interference effect was observed in Raman experiments carried out on isolated SWNTs. The Raman experiment performed on an isolated strained metallic SWNT supports our modeling predictions.

In single-walled carbon nanotubes (SWNTs), their electronic and vibrational structure as well as their charge-carrier dynamics are crucial for potential ultrasmall optical device applications. SWNT properties have now been obtained from optical absorption and time-resolved photoemission and, at the single-nanotube level, by resonance Raman scattering and photoluminescence studies. This article presents an overview of SWNT photophysics, discussing important findings for the characterization of carbon nanotube properties and directions for future research and potential applications. The unique optical properties observed in SWNTs are due to the one-dimensional confinement of electronic states, resulting in van Hove singularities in the nanotube density of states. Optical measurements of phonons, charge-carrier dynamics, and the electronic transition energy van Hove singularities are discussed.

The use of resonance Raman spectroscopy (RRS) to study and characterize single wall carbon nanotubes (SWNTs) is discussed, focusing on preliminary efforts for the development of the RRS to characterize defects in SWNTs. The disorder-induced D-band, disorder-induced peaks just above the first-order allowed graphite G-band, as well as the intermediate frequency modes (IFMs) appearing between the RBM and the D/G spectral region are addressed. RRS on nanographite ribbons and on a step-like defect in highly ordered pyrolytic graphite (HOPG) sheds light into the problem of characterizing specific defects in nano-related carbons.

Optical spectroscopy characterization of carbon nanotube samples requires accurate determination of their band structure and exciton binding energies. In this paper, we present a non-orthogonal density-functional based tight-binding calculation for the electronic transition energies in single-wall carbon nanotubes. We show that the curvature-induced rehybridization of the electronic orbitals, long-range atomic interactions, and geometrical structure relaxation all have a significant impact on the electronic transition energies in the small diameter limit. After including quasiparticle corrections and exciton binding energies, the calculated electronic transition energies show good agreement with the experimental transition energies observed by photoluminescence and resonance Raman spectroscopy.

We present a detailed photoluminescence study of a (6, 5) enriched DNA-wrapped single wall carbon nanotube (DNA-CNT) solid sample and an as-produced DNA-CNT solution. Multiple strong PL peaks were observed at excitation energies that do not correspond to the interband electronic transitions that are strongly enhanced by electronic van Hove singularities. These strong PL peaks are assigned to different mechanisms of excitation and relaxation, including one phonon, two phonon, hot luminescence processes, as well as radiative and non-radiative energy transferring mechanisms between neighboring nanotubes. These processes are assigned to different channels of phonon-assisted electron relaxation. The study shows that the electronic relaxation processes observed in PL can be used as a means to probe different physical interactions between photons, electrons, and phonons that are not separately identified in bulk semiconducting materials.

To better understand the very high thermal conductivity to weight ratio of the graphitic foams recently developed at the Oak Ridge National Laboratory, a Raman spectroscopy study was performed. It was also shown that the Raman scattering can be useful for the characterization of the graphitic foam, being able to evaluate the quality of the samples with respect to the density and location of lattice defects.

Double-walled carbon nanotubes (DWNTs), synthesized by the catalytic decomposition of methane, were explored by resonance Raman spectroscopy using different energies for laser excitation. Based on the radial breathing mode frequencies, the indices of the two layers of a DWNT were approximately assigned, depending on the interlayer separation of the two coaxial layers of the DWNT, which ranged from 0.34 to 0.40 nm. From the tentatively assigned results, it was found that the two walls of the DWNT are not strongly selected by chirality and diameter. The results, however, suggest that, for the tubes that are resonant with the available laser excitation energies, most of the outer layers of the observed DWNTs in our samples are semiconducting, while the inner layers of the observed DWNTs are either semiconducting or metallic based on the assembled DWNTs. The characteristics of the G, D, and G′ band of the DWNTs are discussed, and a double peak feature in the D and G′ band, originating from the inner and outer layers of the DWNTs, is reported.

Low dimensionality provides opportunities to modify the properties of bulk materials dramatically and to control materials properties independently in a manner that is not possible for bulk materials. The special characteristics of low dimensional materials to enhance thermoelectric performance have already been demonstrated in quantum wells, quantum wires and quantum dots. The main focus of this review is a summary of advances made in the modeling of quantum dot superlattice nanowires. Several new research directions for low dimensional thermoelectricity or inspired by this research are briefly mentioned.

An incoherent particle model has been developed to predict the phonon thermal conductivity of nanowires and superlattice nanowires. It is argued that the surface roughness of most real nanowires prevents the formation of idealized confined dispersion relations for typical temperatures and diameters. Instead, the three-dimensional bulk dispersion is used, thus addressing only classical size effects. Four adjustable parameters capture the effects of diameter, superlattice, Umklapp, impurity, and alloy scattering. Predictions are compared with experimental data for nanowires and superlattice nanowires down to 22 nm diameter and 20 K, and are in good agreement above ∼40 nm diameter. The analysis suggests that ideal low thermal conductivity nanowires for thermoelectric applications would have small-diameter, alternating alloy segments that are acoustically dissimilar but electrically similar.

High figure of merit has been reported in superlattice structures in recent years mainly due to a large reduction in thermal conductivity, while maintaining or even enhancing the power factor. These findings suggest the possibility of using nanocomposites to reduce a material's thermal conductivity and thereby increasing the thermoelectric figure of merit. The current work reports on the thermal conductivity of various Si-Ge nanocomposites synthesized in a simple and straightforward process that allows one to exploit nanoscale physics while rapidly producing macroscale devices. Composite synthesis consisted of combining Si nanoparticles approximately 70 nm in diameter with micron-sized Ge particles in various atomic ratios via hotpressing to form macroscale samples. Room-temperature thermal conductivity was measured for each of the nanocomposite samples and compared with the values of SiGe bulk alloys. In this preliminary work, we observed a significant reduction in bulk thermal conductivity in such materials.

The dependences of the thermoelectric properties of (001)KCl/PbTe/SnTe/PbTe three-layer structures on the SnTe layer thickness (dSnTe = 0.5–6.0 nm) at a fixed thickness of PbTe layers were studied. It was established that the thickness dependences of the Seebeck coefficient, the Hall coefficient, electrical conductivity, charge carrier mobility, and the thermoelectric power factor are distinctly non-monotonic. Two possible reasons for this non-monotonic behavior of the thickness dependences of the thermoelectric properties are considered: the size quantization of the energy spectrum in a SnTe quantum well and / or the formation of edge misfit dislocations at the interfaces after reaching the critical thickness, which corresponds to the transition from a pseudomorphic growth to the introduction of misfit dislocations at the interfaces. It is suggested that the observed effect has a general character and should be taken into account when optimizing thermoelectric properties of superlattices.

The optical absorption for ? electrons as a function of the electron wavevector k is investigated by first order perturbation theory in graphite and single wall carbon nanotubes (SWNTs). The matrix element connecting two states in the valence and conduction bands is found to be significantly anisotropic in k-space and polarization dependent. In the case of graphite, the absorption shows a node around the equi-energy contour, and in the case of SWNTs we obtain selection rules that allow only transitions between certain pairs of subbands. The strength of the optical absorption is not only diameter dependent but also chirality dependent. The implications of the optical absorption matrix element on the resonant conditions are discussed.

Three different types of carbon nanotubes being considered for bio-recognition experiments were studied using resonance Raman spectroscopy. Raman spectroscopy, taken using several laser excitation energies, has been shown to provide an effective characterization tool for these carbon nanotubes. The technique yields structural information that both complements and corroborates structural information obtained using electron microscopy techniques, such as TEM, SEM, and AFM.

The possible semiconducting device use of single wall carbon nanotubes (SWNTs) requires a technique for the determination of the exact structure of the nanotubes assembled in the device configuration. Raman spectroscopy has been established as a precise and non-destructive tool for the characterization of graphitic nanostructures. Double resonance theory, which is used to explain the dispersive nature of the Raman bands, has attracted much attention for its potential use for the characterization of the electronic and phonon spectra of these nanostructures. Dispersive features in the Raman spectra of low dimensional graphitic materials, such as carbon nanotubes, can be used to measure directly the anisotropy, or the trigonal warping effect, in the phonon dispersion relations about the hexagonal corner of the Brillouin zone (BZ) of graphite.