Saunab Ghosh

Advanced sorting of single-walled carbon nanotubes by nonlinear density-gradient ultracentrifugation

Existing methods for growing single-walled carbon nanotubes produce samples with a range of structures and electronic properties, but many potential applications require pure nanotube samples. Density-gradient ultracentrifugation has recently emerged as a technique for sorting as-grown mixtures of single-walled nanotubes into their distinct (n,m) structural forms, but to date this approach has been limited to samples containing only a small number of nanotube structures, and has often required repeated density-gradient ultracentrifugation processing. Here, we report that the use of tailored nonlinear density gradients can significantly improve density-gradient ultracentrifugation separations. We show that highly polydisperse samples of single-walled nanotubes grown by the HiPco method are readily sorted in a single step to give fractions enriched in any of ten different (n,m) species. Furthermore, minor variants of the method allow separation of the mirror-image isomers (enantiomers) of seven (n,m) species. Optimization of this approach was aided by the development of instrumentation that spectroscopically maps nanotube contents inside undisturbed centrifuge tubes.

Oxygen Doping Modifies Near-Infrared Band Gaps in Fluorescent Single-Walled Carbon Nanotubes

Better Imaging When Separated A fluorescent probe works better if its absorption and emission wavelengths are well separated; otherwise, the probe tends to reabsorb its own emission. Ghosh et al. (p. 1656, published online 25 November) found that oxygen doping of semiconducting single-wall carbon nanotubes (SWCNTs) improved the characteristics of these materials as imaging probes in the near-infrared. Exposure of SWCNTs to ozone and then to visible light caused the emission wavelength to be 10 to 15% longer than the absorption wavelength. They imaged these probes and untreated SWCNTs in cultured human cells and found an ∼20-fold improvement in contrast. Contrast can be improved in bioimaging applications by separating the emission and absorption wavelengths. Controlled chemical modifications of single-walled carbon nanotubes (SWCNTs) that tune their useful properties have been sought for multiple applications. We found that beneficial optical changes in SWCNTs resulted from introducing low concentrations of oxygen atoms. Stable covalently oxygen-doped nanotubes were prepared by exposure to ozone and then light. Treated samples showed distinct, structure-specific near-infrared fluorescence at wavelengths 10 to 15% longer than displayed by pristine semiconducting SWCNTs. Dopant sites harvest light energy absorbed in undoped nanotube regions by trapping mobile excitons. The oxygen-doped SWCNTs are much easier to detect and image than pristine SWCNTs because they give stronger near-infrared emission and do not absorb at the shifted emission wavelength.

Analyzing Absorption Backgrounds in Single-Walled Carbon Nanotube Spectra

The sources of broad backgrounds in visible-near-IR absorption spectra of single-walled carbon nanotube (SWCNT) dispersions are studied through a series of controlled experiments. Chemical functionalization of nanotube sidewalls generates background absorption while broadening and red-shifting the resonant transitions. Extensive ultrasonic agitation induces a similar background component that may reflect unintended chemical changes to the SWCNTs. No major differences are found between spectral backgrounds in sample fractions with average lengths between 120 and 650 nm. Broad background absorption from amorphous carbon is observed and quantified. Overlapping resonant absorption bands lead to elevated backgrounds from spectral congestion in samples containing many SWCNT structural species. A spectral modeling method is described for separating the background contributions from spectral congestion and other sources. Nanotube aggregation increases congestion backgrounds by broadening the resonant peaks. Essentially no background is seen in sorted pristine samples enriched in a single semiconducting (n,m) species. By contrast, samples enriched in mixed metallic SWCNTs show broad intrinsic absorption backgrounds far from the resonant transitions. The shape of this metallic background component and its absorptivity coefficient are quantitatively assessed. The results obtained here suggest procedures for preparing SWCNT dispersions with minimal extrinsic background absorptions and for quantifying the remaining intrinsic components. These findings should allow improved characterization of SWCNT samples by absorption spectroscopy.

Enrichment of Armchair Carbon Nanotubes via Density Gradient Ultracentrifugation: Raman Spectroscopy Evidence

We have used resonant Raman scattering spectroscopy to fully analyze the relative abundances of different (n,m) species in single-walled carbon nanotube samples that are metallically enriched by density gradient ultracentrifugation. Strikingly, the data clearly show that our density gradient ultracentrifugation process enriches the metallic fractions in armchair and near-armchair species. We observe that armchair carbon nanotubes constitute more than 50% of each (2n + m) family.

Directly Measured Optical Absorption Cross Sections for Structure-Selected Single-Walled Carbon Nanotubes

We have measured peak and spectrally integrated absolute absorption cross sections for the first (E11) and second (E22) optical transitions of seven semiconducting single-walled carbon nanotube (SWCNT) species in bulk suspensions. Species-specific concentrations were determined using short-wave IR fluorescence microscopy to directly count SWCNTs in a known sample volume. Measured cross sections per atom are inversely related to nanotube diameter. E11 cross sections are larger for mod 1 species than for mod 2; the opposite is found for E22.

Efficient spectrofluorimetric analysis of single-walled carbon nanotube samples.

A new method and instrumentation are described for rapid compositional analysis of single-walled carbon nanotube (SWCNT) samples. The customized optical system uses multiple fixed-wavelength lasers to excite NIR fluorescence from SWCNTs individualized in aqueous suspensions. The emission spectra are efficiently captured by a NIR spectrometer with InGaAs multichannel detector and then analyzed by a computer program that consults a database of SWCNT spectral parameters. The identities and relative abundances of semiconducting SWCNTs species are quickly deduced and displayed in graphs and tables. Results are found to be consistent with those based on manual interpretation of full excitation-emission scans from a conventional spectrofluorometer. The new instrument also measures absorption spectra using a broadband lamp and multichannel spectrometers, allowing samples to be automatically characterized by their emission efficiencies. The system provides rapid data acquisition and is sensitive enough to detect the fluorescence of a few picograms of SWCNTs in ~50 μL sample volumes.

Do Inner Shells of Double-Walled Carbon Nanotubes Fluoresce?

The reported fluorescence from inner shells of double-walled carbon nanotubes (DWCNTs) is an intriguing and potentially useful property. A combination of bulk and single-molecule methods was used to study the spectroscopy, chemical quenching, mechanical rigidity, abundance, density, and TEM images of the near-IR emitters in DWCNT samples. DWCNT inner shell fluorescence is found to be weaker than SWCNT fluorescence by a factor of at least 10,000. Observable near-IR emission from DWCNT samples is attributed to SWCNT impurities.

Films of Bare Single-Walled Carbon Nanotubes from Superacids with Tailored Electronic and Photoluminescence Properties

The use of single-walled carbon nanotubes (SWCNTs) in fabricating macroscopic devices requires addressing the challenges of nanotube individualization and organization in the desired functional architectures. Previous success in depositing bare SWCNTs from chlorosulfonic acid onto silicon oxide microporous and mesoporous nanoparticles has motivated this study of their deposition onto fused silica substrates. A facile dip-coating method is reported that produces thin homogeneous films in which the carbon nanotubes are not covered by surfactants or shortened by sonication. Photophysical, electrical, chemical, and morphological properties of these SWCNT films have been characterized. When prepared at low densities, the films exhibit near-IR photoluminescence from individualized SWCNTs, whereas when prepared at high densities the films behave as transparent conductors. Sheet resistance of 471 ohm/sq has been achieved with film transmittance of ∼ 86%.

Structure-Dependent Thermal Defunctionalization of Single-Walled Carbon Nanotubes

Covalent sidewall functionalization of single-walled carbon nanotubes (SWCNTs) is an important tool for tailoring their properties for research purposes and applications. In this study, SWCNT samples were first functionalized by reductive alkylation using metallic lithium and 1-iodododecane in liquid ammonia. Samples of the alkyl-functionalized SWCNTs were then pyrolyzed under an inert atmosphere at selected temperatures between 100 and 500 °C to remove the addends. The extent of defunctionalization was assessed using a combination of thermogravimetric analysis, Raman measurements of the D, G, and radial breathing bands, absorption spectroscopy of the first- and second-order van Hove peaks, and near-IR fluorescence spectroscopy of (n,m)-specific emission bands. These measurements all indicate a substantial dependence of defunctionalization rate on nanotube diameter, with larger diameter nanotubes showing more facile loss of addends. The effective activation energy for defunctionalization is estimated to be a factor of ∼1.44 greater for 0.76 nm diameter nanotubes as compared to those with 1.24 nm diameter. The experimental findings also reveal the quantitative variation with functionalization density of the Raman D/G intensity ratio and the relative near-IR fluorescence intensity. Pyrolyzed samples show spectroscopic properties that are equivalent to those of SWCNTs prior to functionalization. The strong structure dependence of the defunctionalization rate suggests an approach for scalable diameter sorting of mixed SWCNT samples.

Single-walled carbon nanotubes shell decorating porous silicate materials: A general platform for studying the interaction of carbon nanotubes with photoactive molecules

Single-walled carbon nanotubes (SWCNTs) have been deposited onto the external surface of porous silicate materials by deposition from a solution of individualized, protonated SWCNTs in chlorosulfonic acid. It is demonstrated that the deposited SWCNTs can be deprotonated on the silicate surface, yielding a microporous or mesoporous material with individual or small bundles of SWCNTs. These carbon nanotubes present all the spectral characteristics of pristine SWCNTs, including van Hove transitions, Raman and NIR photoluminescence. Furthermore, it is shown that these materials can be used as scaffolds to study the interaction of SWCNTs with photoactive molecules loaded in the cavities of the porous silicate materials. As a proof-of-concept, we showed that the photoluminescence of tris(2,2′-bipyridine)ruthenium(II) can be quenched by protonated SWCNTs in the nearby surface decreasing its lifetime by nearly two orders of magnitude. This represents a novel application for these materials, especially considering the large amount of different molecules that can be immobilized in the internal cavities of these porous silicates.