Novel micro-Raman setup with tunable laser excitation for time-efficient resonance Raman microscopy and imaging.

We describe a micro-Raman setup allowing for efficient resonance Raman spectroscopy (RRS), i.e., mapping of Raman spectra as a function of tunable laser excitation wavelength. The instrument employs angle-tunable bandpass optical filters which are integrated into software-controlled Raman and laser cleanup filter devices. These automatically follow the excitation laser wavelength and combine tunability with high bandpass transmission as well as high off-band blocking of light. Whereas the spectral intervals which can be simultaneously acquired are bandpass limited to ~350 cm(-1), they can be tuned across the spectrum of interest to access all characteristic Raman features. As an illustration of performance, we present Raman mapping of single-walled carbon nanotubes (SWNTs): (i) in a small volume of water-surfactant dispersion as well as (ii) after deposition onto a substrate. A significant improvement in the acquisition time (and efficiency) is demonstrated compared to previous RRS implementations. These results may help to establish (micro) Raman spectral mapping as a routine tool for characterization of SWNTs as well as other materials with a pronounced resonance Raman response in the visible-near-infrared spectral region.

Simultaneous detection of Raman scattering and near-infrared photoluminescence in one imaging microscope.

We describe a microscope which allows simultaneous acquisition of Raman and near-infrared photoluminescence (NIR-PL) spectra and images. The instrument comprises an appropriately modified commercial Raman microscope, utilizes 785 nm excitation laser, and includes two detection channels for Raman and PL within the spectral ranges of ∼787-1000 nm (∼40-2700 cm(-1) Raman shift) and ∼1050-1600 nm, respectively. The configuration can however be easily adapted for other excitation wavelengths and detection ranges. The possibility to simultaneously measure both Raman and NIR-PL spectra - exactly at the same sample locations - can be useful for various applications, for instance, for the characterisation of single-walled carbon nanotubes.

Electroluminescence from chirality-sorted (9,7)-semiconducting carbon nanotube devices.

We have measured the electroluminescence and photoluminescence of (9,7)-semiconducting carbon nanotube devices and demonstrate that the electroluminescence wavelength is determined by the nanotube's chiral index (n,m). The devices were fabricated on Si3N4-membranes by dielectrophoretic assembly of tubes from monochiral dispersion. Electrically driven (9,7)-devices exhibit a single Lorentzian-shaped emission peak at 825 nm in the visible part of the spectrum. The emission could be assigned to the excitonic E22 interband-transition by comparison of the electroluminescence spectra with corresponding photoluminescence excitation maps. We show a linear dependence of the EL peak width on the electrical current, and provide evidence for the inertness of Si3N4 surfaces with respect to the nanotubes optical properties.

Debundling, selection and release of SWNTs using fluorene-based photocleavable polymers.

Photocleavable polymers based on 9,9-dialkylfluorene backbone and o-nitrobenzylether were designed and synthesized to obtain stable (n,m) enriched suspensions of semiconducting SWNTs in toluene. Photoirradiation of the suspensions triggered the precipitation of the SWNTs and TEM images indicate close packing of SWNTs pointing at partial removal of the coating polymer.

Selective bundling of zigzag single-walled carbon nanotubes.

A simple, high throughput fractionation procedure for aqueous/SDS (sodium dodecyl sulfate) suspensions of single-walled carbon nanotubes (SWNTs) is presented, which yields thin bundles of semiconducting-SWNTs with small chiral angles. To demonstrate this we show the photoluminescence signatures of nanotube suspensions that contain almost exclusively zigzag and near-zigzag tubes. Starting suspensions and resulting fractions were characterized using optical absorption, resonance Raman and photoluminescence spectroscopies as well as scanning force microscopy. Taken together with literature observations, our findings suggest that near zigzag edge tubes of similar diameters in a bundle are harder to separate from each other than for other chiral index combinations. We discuss the implications of these observations for SWNT growth and dispersion.

A low-wavenumber-extended confocal Raman microscope with very high laser excitation line discrimination.

We describe the simple modification of a confocal Raman imaging microscope to incorporate two ultra-narrow holographic notch filters. The modified microscope rejects the laser excitation line (Rayleigh peak) by a discrimination factor of ∼10(11) and allows simultaneous measurements of Stokes/anti-Stokes Raman shifts as close as ∼10/20 cm(-1) to the Rayleigh line. The extremely high rejection ratio of the Rayleigh peak results in its intensity becoming comparable to typical Raman scattering signals. This is essential for micro-Raman spectroscopy and imaging in the low-wavenumber region. We illustrate the resulting performance with measurements on silicon/silica, sapphire, sulfur, L-cystine, as well as on single-walled carbon nanotubes (SWNTs). We find that both aggregated (bulk) and individual (deposited on substrate) SWNTs demonstrate strong and broad characteristic Raman features below ∼100 cm(-1)-in a region which has remained essentially unexplored in measurements of bulk SWNT samples and which has so far been inaccessible for Raman spectroscopy of individual SWNTs.

Toward single-chirality carbon nanotube device arrays.

The large-scale integration of devices consisting of individual single-walled carbon nanotubes (SWCNT), all of the same chirality, is a critical step toward their electronic, optoelectronic, and electromechanical application. Here, the authors realize two related goals, the first of which is the fabrication of high-density, single-chirality SWCNT device arrays by dielectrophoretic assembly from monodisperse SWCNT solution obtained by polymer-mediated sorting. Such arrays are ideal for correlating measurements using various techniques across multiple identical devices, which is the second goal. The arrays are characterized by voltage-contrast scanning electron microscopy, electron transport, photoluminescence (PL), and Raman spectroscopy and show identical signatures as expected for single-chirality SWCNTs. In the assembled nanotubes, a large D peak in Raman spectra, a large dark-exciton peak in PL spectra as well as lowered conductance and slow switching in electron transport are all shown to be correlated to each other. By comparison to control samples, we conclude that these are the result of scattering from electronic and not structural defects resulting from the polymer wrapping, similar to what has been predicted for DNA wrapping.

Revisiting the laser dye Styryl-13 as a reference near-infrared fluorophore: implications for the photoluminescence quantum yields of semiconducting single-walled carbon nanotubes.

The near-infrared (NIR) polymethine dye Styryl-13 emitting at approximately 925 nm has recently been suggested as a reference fluorophore for determining the quantum yield (QY) of the NIR photoluminescence of dispersed single-walled carbon nanotubes (SWNTs). Ju et al. reported the QY for SWNTs to be as high as 20% on the basis of 11% QY for Styryl-13 in methanol (Science 2009, 323, 1319). We directly compared the fluorescence of Styryl-13 and Styryl-20 (emitting at approximately 945 nm) with that of the standard fluorophore Rhodamine 6G using a spectrometer with a broad visible-NIR detection range. QYs of 2.0 (4.5) and 0.52 (0.80)% were determined for Styryl-13 and Styryl-20 in methanol (propylene carbonate), respectively. Correspondingly, the above-mentioned photoluminescence efficiency of SWNTs appears to be strongly overestimated. We also discuss singlet oxygen as an alternative NIR reference. A total QY of 1.4% was measured for the emission of singlet oxygen at 1275 nm, as photosensitized by C70 fullerene in air-saturated carbon tetrachloride.