Spectroscopy Of Single-walled Carbon Nanotubes Research Articles

Optical absorption and energy loss spectroscopy of single-walled carbon nanotubes

The recent development of efficient chirality sorting techniques has opened the way to the use of single-walled carbon nanotubes (SWCNTs) in a plethora of nanoelectronic, photovoltaic, and optoelectronic applications. However, to understand the excitation processes undergone by SWCNTs, it is necessary to have highly efficient and accurate computational methods to describe their optical and electronic properties, methods which have until now been unavailable. Here we employ linear combinations of atomic orbitals (LCAOs) to represent the Kohn-Sham (KS) wavefunctions and perform highly efficient time dependent density functional theory (TDDFT) calculations in the frequency domain using our LCAO-TDDFT-$k$-$\omega$ code to model the optical absorbance and energy loss spectra and spatial distribution of the exciton charge densities in SWCNTs. By applying the GLLB-SC derivative discontinuity correction to the KS eigenenergies, we reproduce the measured $E_{11}$ and $E_{22}$ transitions within $\sigma \lesssim 70$ meV and the optical absorbance and electron energy loss spectra semi-quantitatively for a set of fifteen semiconducting and four metallic chirality sorted SWCNTs. Furthermore, our calculated electron hole density difference $\Delta \rho(\textbf{r}, \omega)$ resolves the spatial distribution of the measured excitations in SWCNTs. These results open the path towards the computational design of optimized SWCNT nanoelectronic, photovoltaic, and optoelectronic devices $\textit{in silico}$.

Detection of Circulating Tumor DNA in Human Blood via DNA-Mediated Surface-Enhanced Raman Spectroscopy of Single-Walled Carbon Nanotubes.

The levels of circulating tumor DNA (ctDNA) in the peripheral blood have been associated with tumor burden and malignant progression. However, ultrasensitive detection of ctDNA in blood remains to be explored. Herein, we have developed a new approach, employing DNA-mediated surface-enhanced Raman scattering (SERS) of single-walled carbon nanotubes (SWNTs), that allows ultrasensitive detection of a broad range of ctDNAs in human blood. Combined with the efficient ctDNA recognition capacity of our designed triple-helix molecular switch and RNase HII enzyme-assisted amplification, the T-rich DNA-mediated SERS enhancement of SWNTs could read out a content of KRAS G12DM as low as 0.3 fM, with a detection of 5.0 μL of sample volume, which has potential for point-of-care testing in clinical analysis.

Real-Time Spectroscopy of Single-Walled Carbon Nanotubes for Negative Time Delays by Using a Few-Cycle Pulse Laser

Several investigations using the femtosecond pump−probe technique have been made for coherent phonon dynamics in single-walled carbon nanotubes (SWNTs), which are promising candidates as devices for nanoelectronics and photonics due to their unique properties. However, the most relevant spectroscopic analyses by far have been performed in the positive time range, with the pump pulse coming before the probe. We studied the real-time coherent phonon in SWNTs using 7.1-fs pump−probe measurements for negative time delays in which vibronic coherence between the ground state and exciton state can be observed. Coherent vibrations corresponding to the radial breathing mode caused by the wave packet generated in the exciton state were detected, in contrast to the ground-state wave packet dynamics for positive delays previously reported. The present results show that excited-state wave packets contribute greatly to radial breathing modes in four, (6,5), (6,4), (7,5), and (8,3), chiral systems, but very little to G modes, even though the oscillation period of the latter is 20 fs, which is much shorter than the 100 fs of the exciton life. We discussed the differences in dephasing times in the four different chiral systems.

Photo-induced absorption in the pump probe spectroscopy of single-walled carbon nanotubes

Femtosecond pump probe spectroscopy is employed to study the photo-induced absorption feature in the single-walled carbon nanotube transient spectrum. The two advantages of the experiment, a chirality enriched sample and tuning the pump wavelength to the resonance of a specific nanotube species, greatly facilitate the identification of the photo-induced absorption signal of one tube species. It is found that a photo-induced absorption feature is located at one radial breathing mode to the blue side of the E11 state. This finding prompts a new explanation for the origin of the photo-induced absorption: the transition from the ground state to a phonon coupled state near the Eii state. The explanation suggests a superposition mechanism of the photo-bleach and photo-induced absorption signals, which may serve as a key to the interpretation of the complex pump probe transient spectrum of carbon nanotubes. The finding sheds some light on the understanding of the complex non-radiative relaxation process and the electronic structure of single-walled carbon nanotubes.

Femtosecond excitation correlation spectroscopy of single-walled carbon nanotubes: Analysis based on nonradiative multiexciton recombination processes

We studied the nonlinear time-resolved luminescence signals due to multiexciton recombination processes in single-walled carbon nanotubes (SWNTs) using femtosecond excitation correlation (FEC) spectroscopy. From theoretical analysis of the FEC signals, we found that the FEC signals in the long time range are dominated by the single exciton decay in SWNTs, where the exciton-exciton annihilation process is efficient. Our results provide a simple method to clarify the single exciton decay dynamics in low-dimensional materials.

The Chemistry of Single-Walled Nanotubes

AbstractThe unique structural, electronic, and mechanical properties of single-walled carbon nanotubes (SWNTs) have opened the doors to developments that push the limits of science. These advancements not only further scientific discovery, but also result in the development of everyday practical applications. These applications vary from singlemolecule sensors to nano-scaled transistors to multi-modal biosensors. This article focuses on three distinct developments made as a result of recent advances in spectroscopy of SWNTs. The first system examines the use of SWNTs for molecular detection using near-infrared light to produce tunable fluorescent sensors that are highly photostable. The second system examines the use of a 4-hydroxybenzene diazonium reagent to sort SWNTs based on electronic structure to create on-chip modifications of nano-electronic devices. The third system characterizes nanotube networks for such applications as flexible electronics, exploring the irreversible binding of adsorbates onto nanotube networks using electrical transport and Raman spectroscopy.

Recent Advances in the Optical Spectroscopy of Single-Walled Carbon Nanotubes

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Dielectric properties of single-walled carbon nanotubes in the terahertz frequency range

The authors report on the terahertz time-domain spectroscopy of single-walled carbon nanotubes (SWCNTs) dispersed in a polymer film in a broad frequency range from 0.2to20THz. The complex dielectric function of the composite film is obtained without using Kramers-Kronig analysis, from which the dielectric function of SWCNTs is extracted by using the effective medium theory. The real part of the dielectric function exhibits very large values at low frequency below 2THz. The conductivity spectrum shows a peak around 3THz. The spectral behavior is consistent with overdamped Lorentz oscillator model, indicating the response of curvature-induced small-gap SWCNTs.

Femtosecond Transient Absorption Spectroscopy of Single-Walled Carbon Nanotubes and their Ultrafast Optical Switching Behavior

Two types of individualized single-walled nanotubes (SWNTs) in aqueous surfactant suspensions have been studied by femtosecond two-color absorption spectroscopy. A careful selection of pump and probe wavelengths allows for the determination of the “intrinsic” lifetimes of the lowest excited states which depend on the diameter of the SWNTs. Furthermore, a fast decay component in the ps to sub-ps regime was also observed and tentatively attributed to bundle relaxation. Likewise, this experimental approach can also assess spectral regions with decays faster than 1 ps, which is of great interest for all-optical switching devices near the optical telecommunication wavelength.

High pressure Raman spectroscopy of single-walled carbon nanotubes: Effect of chemical environment on individual nanotubes and the nanotube bundle

Abstract The pressure-induced tangential mode Raman peak shifts for single-walled carbon nanotubes (SWNTs) have been studied using a variety of different solvents as hydrostatic pressure-transmitting media. The variation in the nanotube response to hydrostatic pressure with different pressure transmitting media is evidence that the common solvents used are able to penetrate the interstitial spaces in the nanotube bundle. With hexane, we find the surprising result that the individual nanotubes appear unaffected by hydrostatic pressures (i.e. a flat Raman response) up to 0.7 GPa. Qualitatively similar results have been obtained with butanol. Following the approach of Amer et al. [J. Chem. Phys. 121 (2004) 2752], we speculate that this is due to the inability of SWNTs to adsorb some solvents onto their surface at lower pressures. We also find that the role of cohesive energy density in the solvent–nanotube interaction is more complex than previously thought.

Excitons in Carbon Nanotubes with Broken Time-Reversal Symmetry

Near-infrared magneto-optical spectroscopy of single-walled carbon nanotubes reveals two absorption peaks with an equal strength at high magnetic fields (>55 T). We show that the peak separation is determined by the Aharonov-Bohm phase due to the tube-threading magnetic flux, which breaks the time-reversal symmetry and lifts the valley degeneracy. This field-induced symmetry breaking thus overcomes the Coulomb-induced intervalley mixing which is predicted to make the lowest exciton state optically inactive (or dark).

Long-Lived Charged States in Single-Walled Carbon Nanotubes

We present continuous wave photoinduced absorption spectroscopy of single-walled carbon nanotubes dispersed in a polymer matrix. The spectrum is dominated by a modulation of the absorption line shape, predominantly of large diameter tubes, that we assigned to electroabsorption caused by local electric fields arising from trapped photoinduced charges. The lack of selectivity in the excitation points to an efficient migration of the photoexcited states, either the singlet excitons or the charges resulting from their dissociation.

X-ray absorption near-edge structure and photoelectron spectroscopy of single-walled carbon nanotubes modified by a HBr solution

X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron spectroscopy (PES) have been used to investigate single-walled carbon nanotubes (SWNTs) modified by immersion in a HBr solution at room temperature. After treatment XANES spectra of SWNTs show a new pronounced feature, which has been assigned to new bonds between the sidewall of the SWNTs and Br atoms. This investigation demonstrates the unique capabilities of the XANES spectroscopy as a tool to achieve structural and bonding information of carbon nanotubes induced by chemical processes.

Femtosecond transient absorption spectroscopy of single-walled carbon nanotubes in aqueous surfactant suspensions: Determination of the lifetime of the lowest excited state

Femtosecond one- and two-colour pump-probe spectroscopy of single-walled carbon nanotubes (SWNTs) individual in aqueous surfactant suspensions has been used to assess the "intrinsic" lifetime of the lowest excited states. We demonstrate that such measurements can be perturbed by several competing photophysical processes thus making lifetime deconvolution difficult. Furthermore we show how these effects, arising primarily from sample heterogeneity, can be reduced. Measurements of induced transients in the near IR yield lifetimes of (35 +/- 10) ps and (56 +/- 10) ps, for nanotubes having mean diameters of 0.95 and 1.2 nm, respectively. Furthermore, a fast decay component in the ps to sub-ps regime is also observed. We tentatively attribute this to relaxation in SWNT bundle components.

Fluorescence spectroscopy of single-walled carbon nanotubes in aqueous suspension

Optical studies of single-walled carbon nanotubes have advanced greatly through the recent discovery of near-infrared band gap photoluminescence from single-walled carbon nanotubes (SWNT) isolated in aqueous surfactant suspensions. This fluorescence emission has enabled the detection of many distinct optical transitions and their assignment to specific (n,m) semiconducting species of SWNT. The resulting set of precise transition energies presents a challenge to current theoretical models of nanotube electronic structure and a guide to nanotube researchers using resonance Raman spectroscopy. In the near future, structure-resolved fluorimetry should prove useful for revealing the quantitative (n,m) composition of mixed SWNT samples through sensitive, rapid, and nondestructive measurements. It will also permit detailed studies of many physical and chemical processes that vary with nanotube structure.

Fluorescence spectroscopy of single-walled carbon nanotubes synthesized from alcohol

Near-infrared fluorescence measurements were performed on single-walled carbon nanotubes (SWNTs) catalytically synthesized from alcohol under various experimental conditions (alcohol catalytic CVD method, ACCVD). The chirality distribution was determined by measuring the fluorescence emitted from separated SWNTs as a function of excitation wavelength. Compared with HiPco SWNTs, chiralities of the ACCVD sample were distributed predominantly in the higher chiral angle region, close to the so-called armchair structure. This tendency toward higher chiral angles was more pronounced for smaller diameter nanotubes. The reason for the armchair-rich chirality distribution is discussed based on the initial cap structure satisfying the ‘isolated pentagon rule’.

Ultrahigh-vacuum scanning tunneling microscopy and spectroscopy of single-walled carbon nanotubes on hydrogen-passivated Si(100) surfaces

Single-walled carbon nanotubes (SWNTs) have been studied on a Si(100)-2×1:H surface using an ultrahigh-vacuum (UHV) scanning tunneling microscope (STM). Dry deposition of SWNTs in situ establishes the pristine interface necessary to elucidate fundamental physical and electronic interactions between SWNTs and silicon. We have achieved simultaneous atomic resolution STM images of isolated SWNTs and the local H-passivated Si(100) substrate. Scanning tunneling spectroscopy served to characterize both semiconducting and metallic SWNTs. In each case, electronic features unique to the nanotube can be identified within the substrate band gap. In contrast to previous UHV STM studies of SWNTs on Au(111), our investigation is motivated by the technological relevance of the Si(100) substrate and the potential for nanofabrication of hybrid SWNT-Si electronic devices on the Si(100)-2×1:H platform.

Surface-enhanced and normal stokes and anti-stokes Raman spectroscopy of single-walled carbon nanotubes.

Surface enhancement factors of at least 10(12) for the Raman scattering of single-walled carbon nanotubes in contact with fractal silver colloidal clusters result in measuring very narrow Raman bands corresponding to the homogeneous linewidth of the tangential C-C stretching mode in semiconducting nanotubes. Normal and surface-enhanced Stokes and anti-Stokes Raman spectra are discussed in the framework of selective resonant Raman contributions of semiconducting or metallic nanotubes to the Stokes or anti-Stokes spectra, respectively, of the population of vibrational levels due to the extremely strong surface-enhanced Raman process, and of phonon-phonon interactions.

Transport spectroscopy of single-walled carbon nanotubes

We have performed transport spectroscopy on individual ropes of single-walled carbon nanotubes. We find that the levels are Zeeman split in a magnetic field, with a g-factor of 2.04±0.05. The observed pattern of peak splittings indicates the parity of the number of electrons on the dot. In one device there are also signs of the presence of a second dot. We observe features which resemble anticrossings between quantum levels in the two dots, which may be formed from separate conducting nanotubes within the rope.