Synthesis and raman scattering from Zn(1-x)Mn(x)S diluted magnetic semiconductor nanowires.

The growth of Diluted Magnetic Semiconducting (DMS) Zn(1-x)Mn(x)S (0 < or = x < 0.6) nanowires (NWs) using a three-zone furnace and two solid sources is reported. The approach is generally applicable to many binary and ternary NW systems that grow by the Vapor-Liquid-Solid growth mechanism. Mn concentration was controlled by the temperature of the Mn source. The Zn/Mn ratio was found to determine the crystalline structure, i.e., wurtzite or zinc blende. High-resolution transmission electron microscopy measurements revealed highly crystalline single phase NWs. The vibrational properties of the DMS NWs with different Zn/Mn ratios were studied by correlating their Raman scattering spectra with the composition measured by Energy Dispersive X-Ray Spectroscopy (EDS). We find that the transverse optical (TO) phonon band disappears at the lowest Mn concentrations, while the longitudinal optical (LO) phonon band position was found insensitive to x. Three additional Raman bands were observed between the ZnS q = 0 TO and LO phonons when Mn atoms were present in the NWs. These bands are similar to those reported previously for bulk Zn(1-x)Mn(x)S and their origin is still controversial.

Electronic properties of semiconductor nanowires.

This paper provides a review of the state-of-the-art electronic-structure calculations of semiconductor nanowires. Results obtained using empirical k.p, empirical tight-binding, semi-empirical pseudopotential, and with ab initio methods are compared. For conciseness, we will restrict our detailed discussions to free-standing plain and modulated nanowires. Connections to relevant experimental data, particularly band gaps and polarization anisotropy, will be made since these results depend crucially on the electronic properties. For completeness, a brief review on the synthesis of nanowires is included.

Effect of the tube diameter distribution on the high-temperature structural modification of bundled single-walled carbon nanotubes.

We present results of a systematic high-resolution transmission electron microscopy study of the thermal evolution of bundled single-walled carbon nanotubes (SWNTs) subjected to approximately 4-h high-temperature heat treatment (HTT) in a vacuum at successively higher temperatures up to 2200 degrees C. We have examined purified SWNT material derived from the HiPCO and ARC processes. These samples were found to thermally evolve along very different pathways that we propose depend on three factors: (1) initial diameter distribution, (2) concomitant tightness of the packing of the tubes in a bundle, and (3) the bundle size. Graphitic nanoribbons (GNR) were found to be the dominant high-temperature filament in ARC material after HTT = 2000 degrees C; they were not observed in any heat-treated HiPCO material. The first two major steps in the thermal evolution of HiPCO and ARC material agree with the literature, i.e., coalescence followed by the formation of multiwall carbon nanotubes (MWNTs). However, ARC material evolves to bundled MWNTs, while HiPCO evolves to isolated MWNTs. In ARC material, we find that the MWNTs collapse into multishell GNRs. The thermal evolution of these carbon systems is discussed in terms of the diameter distribution, nanotube coalescence pathways, C-C bond rearrangement, diffusion of carbon and subsequent island formation, as well as the nanotube collapse driven by van der Waals forces.

Raman spectroscopy and structure of crystalline gallium phosphide nanowires.

Gallium phosphide nanowires with a most probable diameter of approximately 20.0 nm and more than 10 microns in length have been synthesized by pulsed laser vaporization of a heated GaP/5% Au target. The morphology and microstructure of GaP nanowires have been investigated by scanning electron microscopy and transmission electron microscopy. Twins have been observed along the crystalline nanowires, which have a growth direction of [111]. Raman scattering shows a 4 cm-1 downshift of the longitudinal optical phonon peak in the nanowire with respect to the bulk; the transverse optical phonon frequency and line width are, however, the same as in the bulk. The quantum confinement model first proposed by Richter et al. cannot explain the observed behavior of the Raman modes.

High-pressure Raman study of debundled single-walled carbon nanotubes.

We report the pressure dependence for the radial (omega R) and tangential (omega T) band frequencies in debundled single-walled carbon nanotubes (SWNTs) derived from laser-synthesized SWNT bundles. As previously described, a chemical procedure was used to prepare debundled SWNTs from as-prepared, large SWNT bundles. The normalized pressure coefficient for omega R in the debundled sample was compared with the corresponding value in the bundled sample to quantify the strength of van der Waals interactions between tubes in these nanotube materials. Furthermore, the pressure dependences for the radial (omega R) and tangential (omega T) band frequencies in debundled tubes were also compared with corresponding dependences predicted for isolated SWNTs, obtained with generalized tight binding molecular dynamic (GTBMD) simulations described in our previous work. The results presented here collectively suggest that the van der Waals interaction is still strong in the debundled sample studied here, which contained predominantly small bundles of SWNTs rather than isolated tubes.

Raman-active modes of single-walled carbon nanotubes derived from the gas-phase decomposition of CO (HiPco process).

Here we report Raman scattering studies of ropes of Single-walled carbon nanotubes (SWNTs) grown by a high CO pressure process. Five samples from five different batches were studied as a function of excitation wavelength. Three of these samples exhibited Raman spectra similar to that found for SWNTs made by pulsed laser vaporization of arc-discharge methods. The other two samples were found by Raman scattering to contain a significant fraction of tubes with diameter < 1.0 nm. These samples exhibited unusual spectra that, however, can be well understood within the existing models for the electronic and phononic states in SWNTs. Spectra recorded with 1064 nm for the sample having a significant fraction of smaller diameter tubes shows strong modes present between 500 and 1200 cm-1. We suggest these modes arise due to the enhancement of Raman cross-section for small diameter tubes.

Electrical properties and far infrared optical conductivity of boron-doped single-walled carbon nanotube films.

Here we report a new approach for producing clean and homogeneous boron-doped single-walled carbon nanotubes. This approach combines the homogeneous dispersion of B(n)O(m)(+) ionic molecules over the nanotube surfaces in a liquid solution, with a high temperature chemical reaction that incorporates the boron atoms into the sp(2) carbon network of the nanotube wall. A comparative study of sheet resistance versus optical transmission in nanotube network films with and without boron-doping is also presented. Although electron energy loss spectroscopy revealed very low B-doping levels (<1 at.%), the dc conductivity of doped samples was raised by a factor of 3.4. Changes in the free carrier contribution to the optical conductivity of single-walled carbon nanotube (SWCNT) films induced by boron-doping was also studied via optical transmission in the far-infrared (IR) (50-7000 cm(-1)). A Drude model was fitted to the changes in the far-IR conductivity to quantify the additional free carrier concentration induced by the B-doping.

Measuring the fluorescent quantum efficiency of indocyanine green encapsulated in nanocomposite particulates.

We present results of a fluorescent quantum efficiency (Φ(F)) study on the encapsulation of the near-infrared dye indocyanine green (ICG) in bioresorbable calcium phosphate nanoparticles (CPNPs). The Φ(F) (described as the ratio of photons emitted to photons absorbed) provides a quantitative means of describing the fluorescence of an arbitrary molecule. However, standard quantum efficiency measurement techniques provide only the Φ(F) of the smallest fluorescing unit-in the case of a nanoparticle suspension, the nanoparticle itself. This presents a problem in accurately describing the Φ(F) of fluorophores embedded in an inorganic nanoparticle. Combining the incidence of scattering with an evaluation of the differences in local electric field and photochemical environment, we have developed a method to determine the Φ(F) of the constituent fluorescent molecules embedded in such a nanoparticle, which provides a more meaningful comparison with the unencapsulated fluorophore. While applicable to generic systems, we present results obtained by our method for the ICG-CPNP in a phosphate buffered 0.15 M saline solution (PBS, pH 7.4)--specifically, Φ(F, free dye) = 0.027 ± 0.001, Φ(F, particle) = 0.053 ± 0.003, and for the individual encapsulated molecules, Φ(F, molecule) = 0.066 ± 0.004. The method developed also provides insight into the influences of encapsulation and key parameters to engineer resonant enhancement effects from the emission of the encapsulated fluorophores corresponding to an eigenmode of the embedding particle for tailored optical properties.

Charge transfer and weak chemisorption of oxygen molecules in nanoporous carbon consisting of a disordered network of nanographene sheets.

The adsorption/desorption processes of oxygen are investigated in nanoporous carbon (activated carbon fiber (ACF)) consisting of a disordered network of nanographene sheets. The heat-induced desorption at 200 °C shows the decomposition of oxygen-including functional groups weakly bonded to nanographene edges. The removal of these oxygen-including negatively charged functional groups brings about a change in the type of majority carriers, from holes to electrons, through charge transfer from the functional groups to the interior of nanographene sheets. The oxygen adsorption brings ACF back to the electronic state with holes being majority carriers. In this process, a large concentration of negatively charged O(2)(δ-) molecules with δ ∼ 0.1 are created through charge transfer from nanographene sheets to the adsorbed oxygen molecules. The changes in the thermoelectric power and the electrical resistance in the oxygen desorption process is steeper than that in the oxygen adsorption process. This suggests the irreversibility between the two processes.

Transparent boron-doped carbon nanotube films.

We report results of studies on the sheet resistance and optical transmission of thin films of boron-doped single-walled carbon nanotubes (SWNTs). Boron doping was carried out by exposure of SWNTs to B 2O 3 and NH 3 at 900 degrees C and 1-3 atom % boron was found in the SWNT bundles via electron energy loss spectroscopy (EELS). Boron doping was found to downshift the positions of the optical absorption bands associated with the van Hove singularities (E 11 (s) E 22 (s) and E 11 (m)) by approximately 30 meV relative to their positions in acid-treated and annealed SWNTs. Raman spectroscopy, EELS, and optical data are consistent with the picture that a few atom % boron has been substituted for carbon in the sp (2) framework of SWNTs. Finally, our results show that boron doping does not significantly affect the optical transmittance in the visible region. However, boron doping lowers the sheet resistance by approximately 30% relative to pristine SWNT films from the same batch. Boron-doped SWNT may provide a better approach to touch-screen technology.

Optical antenna effect in semiconducting nanowires.

We report on investigations of the interaction of light with nanoscale antennae made from crystalline GaP nanowires (NWs). Using Raman scattering, we have observed strong optical antenna effects which we identify with internal standing wave photon modes of the wire. The antenna effects were probed in individual NWs whose diameters are in the range 40 < d < 300 nm. The data and our calculations show that the nature of the backscattered light is critically dependent on the interplay between a photon confinement effect and bulk Raman scattering. At small diameter, d < 65 nm, the NWs are found to act like a nearly perfect dipole antenna and the bulk Raman selection rules are masked leading to a polarized scattering intensity function I R approximately cos4 theta. Underscoring the importance of this work is the realization that a fundamental understanding of the "optical antenna effect" in semiconducting NWs is essential to the analysis of all electro-optic effects in small diameter filaments.

Coherent twinning phenomena: towards twinning superlattices in III-V semiconducting nanowires.

We report evidence in GaP and InP nanowires for a coherent modulation of the structure along the wire axis. By using electron diffraction, we have observed an additional series of diffraction peaks consistent with a quasiperiodic placement of twinning boundaries along the wire. This observation is indeed unexpected, as the vapor-liquid-solid growth conditions used to produce the nanowires were not modulated. The averaged repeat distance of the structure, i.e., the distance between twin boundaries, has been found to depend on the temperature gradient imposed in the growth zone. Future control of the twinning superlattice period should allow significant design possibilities for electronic, thermoelectric, thermal and electro-optic applications of semiconducting nanowires.

Force-deflection spectroscopy: a new method to determine the Young's modulus of nanofilaments.

We demonstrate the determination of Young's modulus of nanowires or nanotubes via a new approach, that is, force-deflection spectroscopy (FDS). An atomic force microscope is used to measure force versus deflection (F-D) curves of nanofilaments that bridge a trench patterned in a Si substrate. The FD data are then fit to the Euler-Bernoulli equation to determine Young's modulus. Our approach provides a generic platform from which to study the mechanical and piezoelectric properties of a variety of materials at the nanoscale level. Young's modulus measurements on ZnS (wurtzite) nanowires are presented to demonstrate this technique. We find that the Young's modulus for rectangular cross section ZnS nanobelts is 52 +/- 7.0 GPa, about 30% smaller than that reported for the bulk.

Raman scattering from high-frequency phonons in supported n-graphene layer films.

Results of room-temperature Raman scattering studies of ultrathin graphitic films supported on Si (100)/SiO2 substrates are reported. The results are significantly different from those known for graphite. Spectra were collected using 514.5 nm radiation on films containing from n = 1 to 20 graphene layers, as determined by atomic force microscopy. Both the first- and second-order Raman spectra show unique signatures of the number of layers in the film. The nGL film analogue of the Raman G-band in graphite exhibits a Lorentzian line shape whose center frequency shifts linearly relative to graphite as approximately 1/n (for n = 1 omegaG approximately 1587 cm-1). Three weak bands, identified with disorder-induced first-order scattering, are observed at approximately 1350, 1450, and 1500 cm-1. The approximately 1500 cm-1 band is weak but relatively sharp and exhibits an interesting n-dependence. In general, the intensity of these D-bands decreases dramatically with increasing n. Three second-order bands are also observed (approximately 2450, approximately 2700, and 3248 cm-1). They are analogues to those observed in graphite. However, the approximately 2700 cm-1 band exhibits an interesting and dramatic change of shape with n. Interestingly, for n < 5 this second-order band is more intense than the G-band.

Confined phonons in Si nanowires.

Raman microprobe studies of long crystalline Si nanowires reveal for the first time the evolution of phonon confinement with wire diameter. The Raman band at approximately 520 cm-1 in bulk Si is found to downshift and asymmetrically broaden to lower frequency with decreasing wire diameter D, in good agreement with a phenomenological model first proposed by Richter et al. An adjustable parameter (alpha) is added to the theory that defines the width of the Gaussian phonon confinement function. We find that this parameter is not sensitive to diameter over the range 4-25 nm.

Thermal conversion of bundled carbon nanotubes into graphitic ribbons.

High temperature heat treatment (HTT) of bundled single-walled carbon nanotubes (SWNTs) in vacuum ( approximately 10(-5) Torr) has been found to lead to the formation of two types of graphitic nanoribbons (GNRs), as observed by high-resolution transmission electron microscopy. Purified SWNT bundles were first found to follow two evolutionary steps, as reported previously, that is, tube coalescence (HTT approximately 1400 degrees C) and then massive bond rearrangement (HTT approximately 1600 degrees C), leading to the formation of bundled multiwall nanotubes (MWNTs) with 3-12 shells. At HTT > 1800 degrees C, we find that these MWNTs collapse into multishell GNRs. The first type of GNR we observed is driven by the collapse of diameter-doubled single-wall nanotubes, and their production is terminated at HTT approximately 1600 degrees C when the MWNTs also start to form. We propose that the collapse is driven by van der Waals forces between adjacent tubes in the same bundle. For HTT > 2000 degrees C, the heat-treated material is found to be almost completely in the multishell GNR form.

Infrared-active vibrational modes of single-walled carbon nanotubes.

The IR-active vibrational modes of single-walled carbon nanotubes have been observed by optical transmission through thin films of bundled nanotubes. Because IR-active chemical functional groups, e.g., -COOH, -OH, might be attached to the tube walls and contribute additional spectral features, we have also studied the effects of chemical purification and long-term high-temperature vacuum annealing on the IR spectrum. Through comparison with theory, we are able to assign much of the sharp structure observed in our IR spectra.

Laser pyrolysis fabrication of ferromagnetic gamma'-Fe4N and FeC nanoparticles.

Using the laser pyrolysis method, single phase gamma'-Fe4N nanoparticles were prepared by a two step method involving preparation of nanoscale iron oxide and a subsequent gas-solid nitridation reaction. Single phase Fe3C and Fe7C3 could be prepared by laser pyrolysis from Fe(CO)5 and 3C2H4 directly. Characterization techniques such as XRD, TEM and vibrating sample magnetometer were used to measure phase structure, particle size and magnetic properties of these nanoscale nitride and carbide particles.

Giant thermopower effects from molecular physisorption on carbon nanotubes.

Results are presented of in situ studies of the thermoelectric power and four-probe resistance of single-walled carbon nanotube films during the adsorption of cyclic hydrocarbons C(6)H(2n) (n=3-6). The size of the change in these transport parameters is found to be related to the pi electron population of the molecule, suggesting the coupling between these pi electrons and those in the nanotube wall may be responsible for the observed effects. A transport model for the SWNT film behavior is presented, incorporating the effects of a new scattering channel associated with the adsorbed molecules.

Chemically doped double-walled carbon nanotubes: cylindrical molecular capacitors.

A double-walled carbon nanotube is used to study the radial charge distribution on the positive inner electrode of a cylindrical molecular capacitor. The outer electrode is a shell of bromine anions. Resonant Raman scattering from phonons on each carbon shell reveals the radial charge distribution. A self-consistent tight-binding model confirms the observed molecular Faraday cage effect, i.e., most of the charge resides on the outer wall, even when this wall was originally semiconducting and the inner wall was metallic.