arXiv subjects

Richard Martel

Publications and source records attributed to Richard Martel.

6 recordsLinked to original sources

arXiv2026

Liquid-phase encapsulation of $\pi$-conjugated dyes in boron nitride nanotubes: Ensemble and single-nanotube optical characterization

Boron nitride nanotubes (BNNTs) provide wide-bandgap, optically transparent one-dimensional hosts for molecular dyes, limiting direct electronic participation of the host. Whether dye@BNNT systems produce bright, well-defined J- or H-aggregates or instead heterogeneous emissive ensembles whose character depends on chain length and local packing remains only partly resolved. We address this question using ensemble extinction, photoluminescence, quantum-yield measurements, and TCSPC-derived radiative and non-radiative rates, together with polarization-resolved single-nanotube microscopy on encapsulated quaterthiophene, sexithiophene, octithiophene, and Nile Red, selected from a ten-dye screening. In the oligothiophene series, confinement modifies spectra and excited-state dynamics in a length-dependent manner, with all three oligothiophenes forming weakly emissive ensembles with suppressed effective radiative rates and 6T showing the strongest redistribution between effective radiative and non-radiative decay. The absence of radiative-rate enhancement or fluorescence-lifetime shortening across the series disfavors bright J-aggregate assignments. Polarization-resolved single-nanotube microscopy reveals strongly polarized emission, but with tube-to-tube and intratube variations, identifying oligothiophene@BNNTs as ordered yet structurally heterogeneous confined ensembles. Nile Red provides a complementary case in which the dominant response is dielectric tuning of a solvatochromic charge-transfer state rather than oligothiophene-like aggregate formation. These findings establish dye-filled BNNTs as optically quiet nanoconfined systems in which molecular ordering, dielectric confinement, and guest-guest coupling can be distinguished through combined ensemble and single-nanotube spectroscopy.

cond-mat.mtrl-sci↗

arXiv2024

Second-Order Raman Scattering in Exfoliated Black Phosphorus

Second-order Raman scattering has been extensively studied in carbon-based nanomaterials, \emph{e.g.} nanotube and graphene, because it activates normally forbidden Raman modes that are sensitive to crystal disorder, such as defects, dopants, strain, etc. The sp$^2$-hybridized carbon systems are, however, the exception among most nanomaterials, where first-order Raman processes usually dominate. Here we report the identification of four second-order Raman modes, named $D_1$, $D_1'$, $D_2$ and $D_2'$, in exfoliated black phosphorus (P(black)), an elemental direct-gap semiconductor exhibiting strong mechanical and electronic anisotropies. Located in close proximity to the $A^1_g$ and $A^2_g$ modes, these new modes dominate at an excitation wavelength of 633 nm. Their evolutions as a function of sample thickness, excitation wavelength, and defect density indicate that they are defect-activated and involve high-momentum phonons in a doubly-resonant Raman process. \emph{Ab initio} simulations of a monolayer reveal that the $D'$ and $D$ modes occur through intravalley scatterings with split contributions in the armchair and zigzag directions, respectively. The high sensitivity of these $D$ modes to disorder helps explaining several discrepancies found in the literature.

cond-mat.mtrl-sci↗

arXiv2021

Infrared Study of Charge Carrier Confinement in Doped (6,5) Carbon Nanotubes

Electronic degrees of freedom and their coupling to lattice vibrations in semiconductors can be strongly modified by doping. Accordingly, the addition of surplus charge carriers to chirality-mixed carbon nanotube samples has previously been found to give rise to a Drude-type plasmon feature as well as Fanotype antiresonances in the far- to mid-infrared spectral range (FIR/MIR). Here we investigate the FIR/MIR response of redox-chemically doped semiconducting (6,5) carbon nanotubes (s-SWNTs). We find that, contrary to expectations, the Drude-type plasmon shifts to lower wavenumbers with increasing doping level. By means of Monte-Carlo simulations of the optical response, we attribute this behavior to the confinement of excess charge carriers at low doping levels and their progressive delocalization when approaching degenerate doping. The coupling of vibrational modes to intraband excitations in the doped s-SWNTs can be probed via a double resonance process similar to that responsible for the Raman D-band. The resulting Fano antiresonances shed new light onto the character and coupling of electronic and vibrational degrees of freedom in these one-dimensional semiconductors.

physics.chem-ph↗

arXiv2015

Phonon-Induced Transparency in Functionalized Single Layer Graphene

Herein, intervalley scattering is exploited to account for anomalous antiresonances in the infrared spectra of doped and disordered single layer graphene. We present infrared spectroscopy measurements of graphene grafted with iodophenyl moieties in both reflection microscopy and transmission configurations. Asymmetric transparency windows at energies corresponding to phonon modes near the Γ and K points are observed, in contrast to the featureless spectrum of pristine graphene. These asymmetric antiresonances are demonstrated to vary as a function of the chemical potential. We propose a model which involves coherent intraband scattering with defects and phonons, thus relaxing the optical selection rule forbidding access to ${\bf q} \neq$ Γ phonons. This interpretation of the new phenomenon is supported by our numerical simulations that reproduce the experimental features.

cond-mat.mes-hall↗

arXiv2015

High field response of gated graphene at THz frequencies

We study the Fermi energy level dependence of nonlinear terahertz (THz) transmission of gated multi-layer and single-layer graphene transferred onto sapphire and quartz substrates. The two samples represent two limits of low-field impurity scattering: short-range neutral and long-range charged impurity scattering, respectively. We observe an increase in the transmission as the field amplitude is increased due to intraband absorption bleaching starting at fields above 8 kV/cm. This effect arises from a field-induced reduction in THz conductivity that depends strongly on the Fermi energy. We account for intraband absorption using a free carrier Drude model that includes neutral and charged impurity scattering as well as optical phonon scattering. We find that although the Fermi-level dependence in the monolayer and five-layer samples is quite different, both exhibit a strong dependence on the field amplitude that cannot be explained on the basis of an increase in the lattice temperature alone. Our results provide a deeper understanding of transport in graphene devices operating at THz frequencies and in modest kV/cm field strengths where nonlinearities exist.

cond-mat.mes-hall↗

arXiv2012

Fano Resonances in Mid-Infrared Spectra of Single-Walled Carbon Nanotubes

This work revisits the physics giving rise to the carbon nanotubes phonon bands in the mid- infrared. Our measurements of doped and undoped samples of single-walled carbon nanotubes in Fourier transform infrared spectroscopy show that the phonon bands exhibit an asymmetric lineshape and that their effective cross-section is enhanced upon doping. We relate these observations to electron-phonon coupling or, more specifically, to a Fano resonance phenomenon. We note that only the dopant-induced intraband continuum couples to the phonon modes and that defects induced in the sidewall increase the resonance probabilities.

cond-mat.mtrl-sci↗