resonance-raman-spectroscopy-of-extreme-nanowires-and-other-1d-systems

Resonance Raman Spectroscopy of Extreme Nanowires and Other 1D Systems

This paper briefly describes how nanowires with diameters corresponding to 1 to 5 atoms can be produced by melting a range of inorganic solids in the ...

University of Nantes CNRS

An optical approach for structural characterization of the modified surface layer in ion-implanted polymers is proposed. The mid-infrared reflectivity from the implanted surface is analyzed in terms of an oscillator dispersion model combined with the theory of differential reflection spectroscopy. The degree of destruction of a specific chemical bond is determined by the relative drop of the oscillator strengths associated with the corresponding vibrational modes. As an example, this methodology is applied to poly(methylmethacrylate) (PMMA) implanted with 50 keV silicon ions at fluences in the range 3 x 10(14) to 1 x 10(17) ions/cm(2). The scission rates for the C=O, C-O-C, and C-H bonds, as well as the static dielectric constant of the ion-modified material, are calculated as a function of the ion fluence. Further, a lower-limit estimate of 120 nm for the thickness of the ion-modified layer is obtained.

Characterization of chemical bonding in ion-implanted polymers by means of mid-infrared reflectivity.

Low-voltage aberration-corrected transmission electron microscopy (AC-TEM) of discrete Lindqvist [W(6)O(19)](2-) polyoxometalate ions inserted from an ethanolic solution of [NBu(4)](2)[W(6)O(19)] into double walled carbon nanotubes (DWNTs) allows a higher precision structural study to be performed than previously reported. W atom column separations within the constituent W(6) tungsten cage can now be visualized with sufficient clarity that reliable correlation with structural predictions from density functional theory (DFT) can be achieved. Calculations performed on [W(6)O(19)](2-) anions encapsulated in carbon nanotubes show good agreement with measured separations between pairs of W(2) atom columns imaged within equatorial WO(6) polyhedral pairs and also single W atom positions located within individual axial WO(6) octahedra. Structural data from the tilted chiral encapsulating DWNT were also determined simultaneously with the anion structural measurements, allowing the influence of the conformation of the encapsulating tubule to be included in the DFT calculation and compared against that of other candidate encapsulating nanotubes. Additional DFT calculations performed using Li(+) cations as a model for the [NBu(4)](+) counterions indicate that the latter may help to induce charge transfer between the DWNT and the [W(6)O(19)](2-) ion and this may help to constrain the motion of the ion in situ.

High-precision imaging of an encapsulated Lindqvist ion and correlation of its structure and symmetry with quantum chemical calculations.

We report a general and simple approach to take control of the color of light-emitting two-luminophore hybrid nanowires (NWs). Our strategy is based on the spatial control at the nanoscale (coaxial geometry) and the spectral selection of the two kinds of luminophores in order to restrict complex charge and energy transfers. Thus, it is possible to control the color of the photoluminescence (PL) as an interpolation of the CIE (Commission Internationale de l'Eclairage) coordinates of each luminophore. For this purpose, we selected a green-emitting semiconducting polymer and a red-emitting hexanuclear metal cluster compound, (n-Bu4N)2Mo6Br8F6, dispersed in a poly(methyl-methacrylate) (PMMA) matrix. The great potential and the versatility of this strategy have been demonstrated for two configurations. First, a yellow PL with a continuous change along the nanowire has been evidenced when the proportion of the PPV shell versus the nanocomposite core, that is, the green/red volumic ratio, progressively shifts from 1:2 to 1:5. Second, an extremely abrupt change in the PL color with red-green-yellow segments has been achieved. A simple model corroborates the effectiveness of this strategy. PL excitation and time-resolved experiments also confirm that no significant charge and energy transfers are involved. The two-luminophore hybrid nanowires may find widespread nanophotonic applications in multicolor emitting sources, lasers and chemical and biological sensors.

Color control in coaxial two-luminophore nanowires.

This paper presents a resonance Raman spectroscopy study of ∼1 nm diameter HgTe nanowires formed inside single walled carbon nanotubes by melt infiltration. Raman spectra have been measured for ensembles of bundled filled tubes, produced using tubes from two separate sources, for excitation photon energies in the ranges 3.39-2.61 and 1.82-1.26 eV for Raman shifts down to ∼25 cm(-1). We also present HRTEM characterization of the tubes and the results of DFT calculations of the phonon and electronic dispersion relations, and the optical absorption spectrum based upon the observed structure of the HgTe nanowires. All of the evidence supports the hypothesis that the observed Raman features are not attributable to single walled carbon nanotubes, i.e., peaks due to radial breathing mode phonons, but are due to the HgTe nanowires. The observed additional features are due to four distinct phonons, with energies 47, 51, 94, and 115 cm(-1), respectively, plus their overtones and combinations. All of these modes have strong photon energy resonances that maximize at around 1.76 eV energy with respect to incident laser.

Raman spectroscopy of optical transitions and vibrational energies of ∼1 nm HgTe extreme nanowires within single walled carbon nanotubes.

The mechanisms that control the photophysics of composite films made of a semiconducting conjugated polymer (poly(paraphenylene vinylene), PPV) mixed with single-walled carbon nanotubes (SWNT) up to a concentration of 64 wt % are determined by using photoexcitation techniques and density functional theory. Charge separation is confirmed experimentally by rapid quenching of PPV photoluminescence and changes in photocurrent starting at relatively low concentrations of SWNT. Calculations predict strong electronic interaction between the polymer and the SWNT network when nanotubes are semiconducting.

Electronic interaction in composites of a conjugated polymer and carbon nanotubes: first-principles calculation and photophysical approaches.

Owing to its high technological importance for optoelectronics, zinc oxide received much attention. In particular, the role of defects on its physical properties has been extensively studied as well as their thermodynamical stability. In particular, a large concentration of Zn vacancies in ZnO bulk materials is so far considered highly unstable. Here we report that the thermal decomposition of zinc peroxide produces wurtzite-type ZnO nanoparticles with an extraordinary large amount of zinc vacancies (>15%). These Zn vacancies segregate at the surface of the nanoparticles, as confirmed by ab initio calculations, to form a pseudo core-shell structure made of a dense ZnO sphere coated by a Zn free oxo-hydroxide mono layer. In others terms, oxygen terminated surfaces are privileged over zinc-terminated surfaces for passivation reasons what accounts for the Zn off-stoichiometry observed in ultra-fine powdered samples. Such Zn-deficient Zn1-xO nanoparticles exhibit an unprecedented photoluminescence signature suggesting that the core-shell-like edifice drastically influences the electronic structure of ZnO. This nanostructuration could be at the origin of the recent stabilisation of p-type charge carriers in nitrogen-doped ZnO nanoparticles.

Eric Faulques

Institut des Matériaux Jean Rouxel

University of Nantes CNRS

Resonance Raman Spectroscopy of Extreme Nanowires and Other 1D Systems