Frank Hennrich

Sidewall Functionalization of Carbon Nanotubes

The addition of nitrenes, nucleophilic carbenes, and radicals affords soluble, individual single-walled nanotubes (shown here is a carbene-functionalized adduct) by covalent sidewall functionalization. The characterization, a fundamental problem in nanotube chemistry, is simple to carry out.

Wideband-tuneable, nanotube mode-locked, fibre laser

Ultrashort-pulse lasers with spectral tuning capability have widespread applications in fields such as spectroscopy, biomedical research and telecommunications. Mode-locked fibre lasers are convenient and powerful sources of ultrashort pulses, and the inclusion of a broadband saturable absorber as a passive optical switch inside the laser cavity may offer tuneability over a range of wavelengths. Semiconductor saturable absorber mirrors are widely used in fibre lasers, but their operating range is typically limited to a few tens of nanometres, and their fabrication can be challenging in the 1.3-1.5 microm wavelength region used for optical communications. Single-walled carbon nanotubes are excellent saturable absorbers because of their subpicosecond recovery time, low saturation intensity, polarization insensitivity, and mechanical and environmental robustness. Here, we engineer a nanotube-polycarbonate film with a wide bandwidth (>300 nm) around 1.55 microm, and then use it to demonstrate a 2.4 ps Er(3+)-doped fibre laser that is tuneable from 1,518 to 1,558 nm. In principle, different diameters and chiralities of nanotubes could be combined to enable compact, mode-locked fibre lasers that are tuneable over a much broader range of wavelengths than other systems.

Chirality distribution and transition energies of carbon nanotubes.

From resonant Raman scattering on isolated nanotubes we obtained the optical transition energies, the radial breathing mode frequency, and the Raman intensity of both metallic and semiconducting tubes. We unambiguously assigned the chiral index (n(1),n(2)) of approximately 50 nanotubes based solely on a third-neighbor tight-binding Kataura plot and find omega(RBM)=(214.4+/-2) cm(-1) nm/d+(18.7+/-2) cm(-1). In contrast to luminescence experiments we observe all chiralities including zigzag tubes. The Raman intensities have a systematic chiral-angle dependence confirming recent ab initio calculations.

Anchoring of rare-earth-based single-molecule magnets on single-walled carbon nanotubes.

A new heteroleptic bis(phthalocyaninato) terbium(III) complex 1, bearing a pyrenyl group, exhibits temperature and frequency dependence of ac magnetic susceptibility, typical of single-molecule magnets. The complex was successfully attached to single-walled carbon nanotubes (SWNTs) using pi-pi interactions, yielding a 1-SWNT conjugate. The supramolecular grafting of 1 to SWNTs was proven qualitatively and quantitatively by high-resolution transmission electron microscopy, emission spectroscopy, and atomic force spectroscopy. Giving a clear magnetic fingerprint, the anisotropy energy barrier and the magnetic relaxation time of the 1-SWNT conjugate are both increased in comparison with the pure crystalline compound 1, likely due to the suppression of intermolecular interactions. The obtained results propose the 1-SWNT conjugate as a promising constituent unit in magnetic single-molecule measurements using molecular spintronics devices.

Doping of single-walled carbon nanotube bundles by Brønsted acids

Using X-ray induced photoelectron spectroscopy, the influence of Bronsted acids, namely sulfuric, nitric, and hydrochloric acid on the electronic properties of single-walled carbon nanotubes (SWCNTs) was investigated. Doping effects were monitored by changes in binding energy of the C 1s core level of the nanotubes. For all three acids, an acceptor type doping of the SWCNTs was observed by a shift of the C 1s core level towards lower binding energies. The inferred change of the Fermi-level position was 0.5 eV in the case of H2SO4, 0.2 eV in the case of HNO3, and 0.1 eV in the case of HCl. For HNO3 and HCl the doping was found to be unstable. The S 2p, N 1s, and Cl 2p core level spectra of the corresponding acid showed spectral features which can be attributed to the respective oxidation state of these anions in the acid, indicating that doping was induced by intercalation.

Single-wall carbon nanotubes with diameters approaching 6 nm obtained by laser vaporization

Abstract Single-wall carbon nanotubes (SWNTs) with large diameters from 2 to 5.6 nm were prepared by pulsed laser vaporization of carbon rods doped with Co, Ni and FeS in an atmosphere of Ar:H2. The SWNT material was characterized by SEM, HRTEM, Raman, IR, UV–VIS–NIR absorption spectroscopy and thermogravimetric analysis.

Preparation of Monodisperse Silicon Nanocrystals Using Density Gradient Ultracentrifugation

We report the preparation of monodisperse silicon nanocrystals (ncSi) by size-separation of polydisperse alkyl-capped ncSi using organic density gradient ultracentrifugation. The ncSi were synthesized by thermal processing of trichlorosilane-derived sol-gel glasses followed by HF etching and surface passivation with alkyl chains and were subsequently fractionated by size using a self-generating density gradient of 40 wt % 2,4,6-tribromotoluene in chlorobenzene. The isolated monodisperse fractions were characterized by photoluminescence spectroscopy and high-angle annular dark-field scanning transmission electron microscopy and determined to have polydispersity index values between 1.04 and 1.06. The ability to isolate monodisperse ncSi will allow for the quantification of the size-dependent structural, optical, electrical, and biological properties of silicon, which will undoubtedly prove useful for tailoring property-specific optoelectronic and biomedical devices.

Selective Dispersion of Single-Walled Carbon Nanotubes with Specific Chiral Indices by Poly(N-decyl-2,7-carbazole)

Physico-chemical methods to sort single-walled carbon nanotubes (SWNTs) by chiral index are presently lacking but are required for in-depth experimental analysis and also for potential future applications of specific species. Here we report the unexpected selectivity of poly(N-decyl-2,7-carbazole) to almost exclusively disperse semiconducting SWNTs with differences of their chiral indices (n - m) ≥ 2 in toluene. The observed selectivity complements perfectly the dispersing features of the fluorene analogue poly(9,9-dialkyl-2,7-fluorene), which disperses semiconducting SWNTs with (n - m) ≤ 2 in toluene. The dispersed samples are further purified by density gradient centrifugation and analyzed by photoluminescence excitation spectroscopy. All-atom molecular modeling with decamer model compounds of the polymers and (10,2) and (7,6) SWNTs suggests differences in the π-π stacking interaction as origin of the selectivity. We observe energetically favored complexes between the (10,2) SWNT and the carbazole decamer and between the (7,6) SWNT and the fluorene decamer, respectively. These findings demonstrate that subtle structural changes of polymers lead to selective solvation of different families of carbon nanotubes. Furthermore, chemical screening of closely related polymers may pave the way toward simple, low-cost, and index-specific isolation of SWNTs.

Electroluminescence from a single nanotube-molecule-nanotube junction

The positioning of single molecules between nanoscale electrodes has allowed their use as functional units in electronic devices. Although the electrical transport in such devices has been widely explored, optical measurements have been restricted to the observation of electroluminescence from nanocrystals and nanoclusters and from molecules in a scanning tunnelling microscope setup. In this Letter, we report the observation of electroluminescence from the core of a rod-like molecule between two metallic single-walled carbon nanotube electrodes forming a rigid solid-state device. We also develop a simple model to explain the onset voltage for electroluminescence. These results suggest new characterization and functional possibilities, and demonstrate the potential of carbon nanotubes for use in molecular electronics.

L-band ultrafast fiber laser mode locked by carbon nanotubes

We fabricate a nanotube-polyvinyl alcohol saturable absorber with a broad absorption at 1.6 μm. We demonstrate a pulsed fiber laser working in the telecommunication L band by using this composite as a mode locker. This gives ∼498±16 fs pulses at 1601 nm with a 26.7 MHz repetition rate.