Exciton energy transfer in nanotube bundles

Photoluminescence is commonly used to identify the electronic structure of individual nanotubes. But, nanotubes naturally occur in bundles. Thus, we investigate photoluminescence of nanotube bundles. We show that their complex spectra are simply explained by exciton energy transfer between adjacent tubes, whereby excitation of large gap tubes induces emission from smaller gap ones via Forster interaction between excitons. The consequent relaxation rate is faster than non-radiative recombination, leading to enhanced photoluminescence of acceptor tubes. This fingerprints bundles with different compositions and opens opportunities to optimize them for opto-electronics.Comment: 5 pages, 5 figure

Method for separating single-wall carbon nanotubes and compositions thereof

The invention relates to a process for sorting and separating a mixture of (n, m) type single-wall carbon nanotubes according to (n, m) type. A mixture of (n, m) type single-wall carbon nanotubes is suspended such that the single-wall carbon nanotubes are individually dispersed. The nanotube suspension can be done in a surfactant-water solution and the surfactant surrounding the nanotubes keeps the nanotube isolated and from aggregating with other nanotubes. The nanotube suspension is acidified to protonate a fraction of the nanotubes. An electric field is applied and the protonated nanotubes migrate in the electric fields at different rates dependent on their (n, m) type. Fractions of nanotubes are collected at different fractionation times. The process of protonation, applying an electric field, and fractionation is repeated at increasingly higher pH to separated the (n, m) nanotube mixture into individual (n, m) nanotube fractions. The separation enables new electronic devices requiring selected (n, m) nanotube types

Intersubband decay of 1-D exciton resonances in carbon nanotubes

We have studied intersubband decay of E22 excitons in semiconducting carbon nanotubes experimentally and theoretically. Photoluminescence excitation line widths of semiconducting nanotubes with chiral indicess (n, m) can be mapped onto a connectivity grid with curves of constant (n-m) and (2n+m). Moreover, the global behavior of E22 linewidths is best characterized by a strong increase with energy irrespective of their (n-m) mod(3)= \pm 1 family affiliation. Solution of the Bethe-Salpeter equations shows that the E22 linewidths are dominated by phonon assisted coupling to higher momentum states of the E11 and E12 exciton bands. The calculations also suggest that the branching ratio for decay into exciton bands vs free carrier bands, respectively is about 10:1.Comment: 4 pages, 4 figure

Electrical properties of boron-doped MWNTs synthesized by hot-filament chemical vapor deposition

We have synthesized a large amount of boron-doped multiwalled carbon nanotubes (MWNTs) by hot-filament chemical vapor deposition. The synthesis was carried out in a flask using a methanol solution of boric acid as a source material. The scanning electron microscopy, transmission electron microscopy, and micro-Raman spectroscopy were performed to evaluate the structural properties of the obtained MWNTs. In order to evaluate the electrical properties, temperature dependence of resistivity was measured in an individual MWNTs with four metal electrodes. The Ramman shifts suggest carrier injection into the boron-doped MWNTs, but the resistivity of the MWNTs was high and increased strongly with decreasing temperature. Defects induced by the plasma may cause this enhanced resistivity.Comment: 16 pages, 5 figures; submitted to the Proceedings of 21st International Symposium on Superconductivity, Tsukuba, Japan, October 27-29, 200

Electronic Devices Based on Purified Carbon Nanotubes Grown By High Pressure Decomposition of Carbon Monoxide

The excellent properties of transistors, wires, and sensors made from single-walled carbon nanotubes (SWNTs) make them promising candidates for use in advanced nanoelectronic systems. Gas-phase growth procedures such as the high pressure decomposition of carbon monoxide (HiPCO) method yield large quantities of small diameter semiconducting SWNTs, which are ideal for use in nanoelectronic circuits. As-grown HiPCO material, however, commonly contains a large fraction of carbonaceous impurities that degrade properties of SWNT devices. Here we demonstrate a purification, deposition, and fabrication process that yields devices consisting of metallic and semiconducting nanotubes with electronic characteristics vastly superior to those of circuits made from raw HiPCO. Source-drain current measurements on the circuits as a function of temperature and backgate voltage are used to quantify the energy gap of semiconducting nanotubes in a field effect transistor geometry. This work demonstrates significant progress towards the goal of producing complex integrated circuits from bulk-grown SWNT material.Comment: 6 pages, 4 figures, to appear in Nature Material

Self-assembled nanoscale photomimetic models: structure and related dynamics

Using static and time-resolved measurements, dynamics of non-radiative relaxation processes have been studied in self-assembled porphyrin triads of various geometry, containing the main biomimetic components, Zn–porphyrin dimers, free-base extra-ligands (porphyrin, chlorin or tetrahydroporphyrin), and electron acceptors A (quinone or pyromellitimide). The strong quenching of the dimer fluorescence is due to energy and sequential electron transfer (ET) processes to the extra-ligand (~0.9–1.7 ps), which are faster than a slower ET (34–135 ps) from the dimer to covalently linked A in toluene at 293 K. The extra-ligand S₁-state decay (τₛ = 940–2670 ps) is governed by competing processes: a bridge (dimer) mediated long-range (r_DA = 18–24 Å) superexchange ET to an acceptor, and photoinduced hole transfer from the excited extra-ligand to the dimer followed by possible superexchange ET steps to low-lying charge transfer states of the triads. The subsequent ET steps dimer → monomer → A taking place in the triads, mimic the sequence of primary ET reactions in photosynthetic reaction centers in vivo. © 2002 Elsevier Science B.V. All rights reserved

Competition between electron transfer and energy migration in self-assembled porphyrin triads

The photoinduced electron transfer (ET) and the energy migration (EM) processes have been studied in liquid solutions and polymeric (PMMA) films for the triads consisting of the Zn-octaethylporphyrin chemical dimer (the energy and electron donor, D) and dipyridyl substituted tetrapyrrole extra-ligands (porphyrins, chlorin, tetrahydroporphyrin) as the acceptors, A. On the basis of the time correlated single photon counting technique and femtosecond pump-probe spectroscopy, it has been shown that D fluorescence quenching with time constant ranging from 1.7 to 10 ps is due to competing EM and ET processes from the dimer to A's. In addition, the fluorescence decay time shortening (by ∼1.3–1.6 times in toluene at 293 K) is observed for electron accepting extra-ligands in the triads. The acceptor fluorescence quenching is hard dependent on the mutual spatial arrangement of the triad subunits, but becomes stronger upon the solvent polarity increase (addition of acetone to toluene solutions) as well as the temperature lowering (from 278 to 221 K). The possible reasons and mechanisms of the non-radiative deactivation of locally excited S₁-states in the triads are discussed taking into account a close lying charge-separated state. The obtained experimental data are analyzed using the reduced density matrix formalism in the frame of Haken–Strobl–Reineker approach. This model includes EM and ET processes as well as the dephasing of coherence between the excited electronic states of the triad. © 2001 Elsevier Science B.V. All rights reserved

Electron transfer in porphyrin multimolecular self-organized nanostructures

On the base of of covalent and non-covalent bonds nanoscale self-assembling multiporphyrin arrays with well-defined geometry, the controllable number of interacting components and their spectral and photophysical properties were formed. The deactivation of excited singlet and triplet states was studied using steady-state, time-resolved picosecond fluorescence (∆½≈30 ps) and femtosecond pump-probe (∆½≈280 fs) spectroscopy in solvents of various polarity at 77-300 K. It has been found that the competition between the non-radiative energy transfer (within ≤10 ps) and charge transfer (within 300 fs - 700 ps) processes in the systems depends on the structure, spectral and redox properties of interacting subunits and may be driven by the distance, temperature and solvent polarity. The possible pathways and mechanisms of the electron transfer in the systems of various types are discussed (Marcus theory for the “normal” region and the non-adiabatic case, the “superexchange” mechanism)

Photoinduced electron transfer dynamics for self-assembled porphyrin arrays in solutions and films

Electronic excitation energy deactivation in self-assembled porphyrin triads has been studied by the time correlated single photon counting technique as a function of the solvent polarity (toluene-acetone mixtures), temperature (77-350 K), and mutual spatial arrangement of the donor and acceptor subunits. The donor (Zn-octaethylporphyrin chemical dimer) fluorescence quenching with time constant of 1.7÷10 ps is due to competing energy migration and electron transfer processes to the acceptor (dipyridyl substituted tetrapyrrole extra-ligand). The quenching of the acceptor fluorescence (by ~ 1.3–1.6 times) does not significantly depend on the mutual spatial arrangement of the triad subunits and increases with the solvent polarity rising and the decrease of the temperature. The obtained experimental data are analyzed using the reduced density matrix formalism in the frame of Haken-Strobl-Reineker approach taking into account the energy transfer, charge separation, and the dephasing of coherence between the excited electronic states of the triad

Steric interactions influence on electron transfer efficiency in meso-nitrophenylporphyrins and their chemical dimers

Steric interactions upon mono- and di-meso-phenyl substitution in octaethylporphyrins (OEP) and their chemical dimers with the phenyl spacer manifests itself in the dramatical T₁-state lifetimes shortening at 293 K (from ms down to μs in degassed toluene solutions) without any influence on spectral-kinetic parameters of S₀- and S₁-states. This effect is explained by non-planar dynamic conformations in excited T₁-states caused by the phenyl ring torsional librations around a single C-C bond. For meso-ortho-nitrophenyl substituted OEPs the S₁-state quenching is caused by the direct “through space” electron transfer to low-lying CT state while for the corresponding Pd-complexes the direct electron transfer takes place from the locally excited T₁-state. For the last two cases steric interactions provide the optimal geometry with high electronic coupling between porphyrin macrocycle and nitro-group