31 research outputs found
Unifying the low-temperature photoluminescence spectra of carbon nanotubes: the role of acoustic phonon confinement
At low temperature the photoluminescence of single-wall carbon nanotubes show
a large variety of spectral profiles ranging from ultra narrow lines in
suspended nanotubes to broad and asymmetrical line-shapes that puzzle the
current interpretation in terms of exciton-phonon coupling. Here, we present a
complete set of photoluminescence profiles in matrix embedded nanotubes
including unprecedented narrow emission lines. We demonstrate that the
diversity of the low-temperature luminescence profiles in nanotubes originates
in tiny modifications of their low-energy acoustic phonon modes. When low
energy modes are locally suppressed, a sharp photoluminescence line as narrow
as 0.7 meV is restored. Furthermore, multi-peak luminescence profiles with
specific temperature dependence show the presence of confined phonon modes
Chirality dependence of the absorption cross-section of carbon nanotubes
The variation of the optical absorption of carbon nanotubes with their
geometry has been a long standing question at the heart of both metrological
and applicative issues, in particular because optical spectroscopy is one of
the primary tools for the assessment of the chiral species abundance of
samples. Here, we tackle the chirality dependence of the optical absorption
with an original method involving ultra-efficient energy transfer in
porphyrin/nanotube compounds that allows uniform photo-excitation of all chiral
species. We measure the absolute absorption cross-section of a wide range of
semiconducting nanotubes at their S22 transition and show that it varies by up
to a factor of 2.2 with the chiral angle, with type I nanotubes showing a
larger absorption. In contrast, the luminescence quantum yield remains almost
constant
Intraband and intersubband many-body effects in the nonlinear optical response of single-wall carbon nanotubes
International audienceWe report on the nonlinear optical response of a mono-chiral sample of (6,5) single-wall carbon nanotubes by means of broad-band two-color pump-probe spectroscopy with selective excitation of the S11 excitons. By using a moment analysis of the transient spectra, we show that all the nonlinear features can be accurately accounted for by elementary deformations of the linear absorption spectrum. The photo-generation of S11 excitons induces a broadening and a blue shift of both the S11 and S22 excitonic transitions. In contrast, only the S11 transition shows a reduction of oscillator strength, ruling out population up-conversion. These nonlinear signatures result from many-body effects, including phase-space filling, wave-function renormalization and exciton collisions. This framework is sufficient to interpret the magnitude of the observed nonlinearities and stress the importance of intersubband exciton interactions. Remarkably, we show that these intersubband interactions have the same magnitude as the intraband ones and bring the major contribution to the photo-bleaching of the S22 excitonic transition upon S11 excitation through energy shift and broadening
Ultrafast nano generation of acoustic waves in water via a single carbon nanotube
Generation of ultra high frequency acoustic waves in water is key to nano resolution sensing, acoustic imaging and theranostics. In this context water immersed carbon nanotubes (CNTs) may act as an ideal optoacoustic source, due to their nanometric radial dimensions, peculiar thermal properties and broad band optical absorption. The generation mechanism of acoustic waves in water, upon excitation of both a single -wall (SW) and a multi-wall (MW) CNT with laser pulses of temporal width ranging from 5 ns down to ps, is theoretically investigated via a multiscale approach. We show that, depending on the combination of CNT size and laser pulse duration, the CNT can act as a thermophone or a mechanophone. As a thermophone, the CNT acts as a nanoheater for the surrounding water, which, upon thermal expansion, launches the pressure wave. As a mechanophone, the CNT acts as a nanopiston, its thermal expansion directly triggering the pressure wave in water. Activation of the mechanophone effect is sought to trigger few nanometers wavelength sound waves in water, matching the CNT acoustic frequencies. This is at variance with respect to the commonly addressed case of water-immersed single metallic nano-objects excited with ns laser pulses, where only the thermophone effect significantly contributes. The present findings might be of impact in fields ranging from nanoscale non-destructive testing to water dynamics at the meso to nanoscale
Dissociation of two-dimensional excitons in monolayer WSe<sub>2</sub>
In two-dimensional semiconductors excitons are strongly bound, suppressing the creation of free carriers. Here, the authors investigate the main exciton dissociation pathway in p-n junctions of monolayer WSe2 by means of time and spectrally resolved photocurrent measurements
Interaction between carbon nanotubes and their physico-chemical environment : towards the control of the optical properties
Cette thèse est consacrée à l'étude expérimentale par spectroscopie de photoluminescence de nanotubes de carbone nus et fonctionnalisés. Les nanotubes étant formés exclusivement d'atomes de surface, leurs propriétés optiques peuvent être grandement altérées, mais aussi contrôlées, par interaction avec l'environnement physico-chimique. Un dispositif de microscopie confocale à l'échelle de l'objet unique et à température cryogénique est développé pour l'étude de la luminescence de nanotubes déposés sur substrat. La variété des profils spectraux observés est interprétée en terme d'un couplage entre excitons localisés et phonons acoustiques unidimensionnels dont le spectre peut être altéré aux basses énergies. Ce mécanisme explique notamment l'observation originale de raies très fines, de largeur inférieure à 500 µeV. La fonctionnalisation non-covalente des nanotubes par des molécules de colorants (porphyrines) introduit une nouvelle voie d'excitation optique par un transfert d'énergie très efficace. Le suivi physico-chimique de la réaction d'adsorption nous informe sur la couverture et l'affinité des molécules sur les nanotubes. Une étude de photoluminescence sur composés uniques résolue en polarisation montre une forte anisotropie du transfert d'énergie gouvernée par des effets d'antenne à proximité du nanotube. Enfin, le colorant peut être utilisé comme cellule d'absorption de référence pour évaluer la section efficace d'absorption des nanotubes. Une nette évolution avec l'angle chiral de l'espèce est notamment observée pour l'absorption à la résonance optique S22.This manuscript presents an experimental study on pristine and functionalized single-wall carbon nanotubes by means of photoluminescence spectroscopy. Due to nanotubes original one-layer structure, the physico-chemical environment can greatly alter their optical properties, introducing in the same time a way to control these properties. Luminescence signals from single substrate desposited nanotubes are studied with a home-made confocal microscope at cryogenic temperatures. The large variety of observed spectral profiles is interpreted in term of an unified coupling between localized excitons and unidimensionnal acoustic phonons. In particular, a local gap in the low energy phonon spectrum leads to narrow lines with width lower than 500 µeV. Nanotubes non-covalently functionalized with dye molecules (porphyrins) show an original absorption feature at 2.8 eV involving a very efficient energy transfer. Molecules coverage and affinity on the nanotube wall are evaluated from the adsorption thermodynamic equilibrium. A polarized photoluminescence study at the single compound scale reveals that the energy transfer shows strong anisotropy owing to antenna effects in the vicinity of the nanotube. Finally, the dye molecule can be used as an absorptive unit cell to calculate the absorption cross section of carbon nanotubes. A clear evolution is found at the S22 optical resonance with respect to the chiral angle of the species
Interaction entre les nanotubes de carbone et leur environnement physico-chimique : vers un contrôle des propriétés optiques
This manuscript presents an experimental study on pristine and functionalized single-wall carbon nanotubes by means of photoluminescence spectroscopy. Due to nanotubes original one-layer structure, the physico-chemical environment can greatly alter their optical properties, introducing in the same time a way to control these properties. Luminescence signals from single substrate desposited nanotubes are studied with a home-made confocal microscope at cryogenic temperatures. The large variety of observed spectral profiles is interpreted in term of an unified coupling between localized excitons and unidimensionnal acoustic phonons. In particular, a local gap in the low energy phonon spectrum leads to narrow lines with width lower than 500 µeV. Nanotubes non-covalently functionalized with dye molecules (porphyrins) show an original absorption feature at 2.8 eV involving a very efficient energy transfer. Molecules coverage and affinity on the nanotube wall are evaluated from the adsorption thermodynamic equilibrium. A polarized photoluminescence study at the single compound scale reveals that the energy transfer shows strong anisotropy owing to antenna effects in the vicinity of the nanotube. Finally, the dye molecule can be used as an absorptive unit cell to calculate the absorption cross section of carbon nanotubes. A clear evolution is found at the S22 optical resonance with respect to the chiral angle of the species.Cette thèse est consacrée à l'étude expérimentale par spectroscopie de photoluminescence de nanotubes de carbone nus et fonctionnalisés. Les nanotubes étant formés exclusivement d'atomes de surface, leurs propriétés optiques peuvent être grandement altérées, mais aussi contrôlées, par interaction avec l'environnement physico-chimique. Un dispositif de microscopie confocale à l'échelle de l'objet unique et à température cryogénique est développé pour l'étude de la luminescence de nanotubes déposés sur substrat. La variété des profils spectraux observés est interprétée en terme d'un couplage entre excitons localisés et phonons acoustiques unidimensionnels dont le spectre peut être altéré aux basses énergies. Ce mécanisme explique notamment l'observation originale de raies très fines, de largeur inférieure à 500 µeV. La fonctionnalisation non-covalente des nanotubes par des molécules de colorants (porphyrines) introduit une nouvelle voie d'excitation optique par un transfert d'énergie très efficace. Le suivi physico-chimique de la réaction d'adsorption nous informe sur la couverture et l'affinité des molécules sur les nanotubes. Une étude de photoluminescence sur composés uniques résolue en polarisation montre une forte anisotropie du transfert d'énergie gouvernée par des effets d'antenne à proximité du nanotube. Enfin, le colorant peut être utilisé comme cellule d'absorption de référence pour évaluer la section efficace d'absorption des nanotubes. Une nette évolution avec l'angle chiral de l'espèce est notamment observée pour l'absorption à la résonance optique S22
One-step grown suspended single walled carbon nanotubes (SWNTS) by plasma enhanced chemical vapor deposition
Communication oraleInternational audienceSuspended single-walled carbon nanotubes were grown only on predefined place of three dimensional structures for future nanotechnology applications . We demonstrated the in situ one-step growth of SWNTs by an electron cyclotron resonance (ECR) CVD method at low temperature (650°C) and low ethylene pressure ( 2x10-3 mbar)[1]. Catalytic Fe or Fe2O3 nanoparticles were directly deposited on Si pillars using a reactive sputtering ECR plasma. SWNTs were originally grown from catalysts on top of the pillars and finished on another silicon pillar or TiN electrode (Fig. 1). Raman scattering in a confocal microscopy setup has been used to measure the RBMs of SWNTs (Fig.2) therefore allowing the diameter distribution identification. We found that very narrow tubes (d<0.8nm) represent a significant amount of the suspended nanotubes. The G and D bands were also observed leading information on respectively, the metallic or semi-conducting nature of the individual nanotubes and their excellent crystallographic quality. Photo-luminescence microscopy will be used to identify individual SWNTs and to determine their chiral indices and study the excitonic diffusion dynamics in this very specific as grown suspended geometry. References [1] M. Delaunay, A. Senillou and M.N. Semeria, U.S. Patent n° US 7,160,585 B2-Jan. 9,200