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International audience; The fast relaxation processes in the excited electronic states of functionalized aza-boron-dipyrromethene (aza-BODIPY) derivatives (1-4) were investigated in liquid media at room temperature, including the linear photophysical, photochemical, and nonlinear optical (NLO) properties. Optical gain was revealed for nonfluorescent derivatives 3 and 4 in the near infrared (NIR) spectral range under femtosecond excitation. The values of two-photon absorption (2PA) and excited-state absorption (ESA) cross-sections were obtained for 1-4 in dichloromethane using femtosecond Z-scans, and the role of bromine substituents in the molecular structures of 2 and 4 is discussed. The nature of the excited states involved in electronic transitions of these dyes was investigated using quantum-chemical TD-DFT calculations, and the obtained spectral parameters are in reasonable agreement with the experimental data. Significant 2PA (maxima cross-sections ∼2000 GM), and large ESA cross-sections ∼10(-20) m(2) of these new aza-BODIPY derivatives 1-4 along with their measured high photostability reveal their potential for photonic applications in general and optical limiting in particular.

Space-time (ST) wave packets are a class of pulsed optical beams whose spatio-temporal spectral structure results in propagation invariance, tunable group velocity, and fascinating refractive phenomena. Here, we investigate the refraction of ST wave packets at a planar interface between two dispersive, homogeneous, isotropic media. We formulate a new refractive invariant for ST wave packets in this configuration, from which we obtain a law of refraction that determines the change in their group velocity across the interface. We verify this new refraction law in ZnSe and CdSe, both of which manifest large chromatic dispersion at near-infrared frequencies in the vicinity of their band edges. ST wave packets can thus be a tool in nonlinear optics for bridging large group-velocity mismatches in highly dispersive scenarios., 5 pages, 4 figures

International audience; Aza-boron dipyrromethenes (aza-BODIPYs) presenting a benzothiadiazole substitution on upper positions are described. The strong electron-withdrawing effect of the benzothiadiazole moiety permits enhancement of the accepting strength and improves the delocalization of the aza-BODIPY core to attain a significant degree of electronic communication between the lower donating groups and the upper accepting groups. The nature of the intramolecular charge transfer is studied both experimentally and theoretically. Linear spectroscopy highlighted the strongly redshifted absorption and emission of the synthesized molecules with recorded fluorescence spectra over 1000 nm. Nonlinear optical properties were also investigated. Strong enhancement of the two-photon absorption of the substituted dyes compared with the unsubstituted one (up to 4520 GM at 1300 nm) results in an approximately 15-20 % improvement of the optical power limiting performances. These dyes are therefore a good starting point for further improvement of optical power limiting in the short-wave IR range.

This paper presents three-photon absorption (3PA) measurement results for nine direct-gap semiconductors, including full 3PA spectra for ZnSe, ZnS, and GaAs. These results, along with our theory of 3PA using an 8-band Kane model (4 bands with double spin degeneracy), help to explain the significant disagreements between experiments and theory in the literature to date. 3PA in the 8-band model exhibits quantum interference between the various possible pathways that is not observed in previous 2-band theories. We present measurements of degenerate 3PA coefficients in InSb, GaAs, CdTe, CdSe, ZnTe, CdS, ZnSe, ZnO, and ZnS. We examine bandgap, Eg, scaling using 2-band tunneling and perturbation theories that show agreement with the predicted Eg^-7 dependence; however, For those semiconductors for which we measured full 3PA spectra, we observe significant discrepancies with both 2-band theories. On the other hand, our 8-band model shows excellent agreement with the spectral data. We then use our 8-band theory to predict the 3PA spectra for 15 different semiconductors in their zincblende form. These results allow prediction and interpretation of the 3PA coefficients for various narrow to wide bandgap semiconductors., 20 pages

Gold dipole nanoantennas embedded in an organic molecular film provide strong local electromagnetic fields to enhance both the nonlinear refractive index (n2) and two-photon absorption (2PA) of the molecules. An enhancement of 53× for 2PA and 140× for nonlinear refraction is observed for BDPAS (4,4′-bis(diphenylamino)stilbene) at 600 nm with only 3.7% of gold volume fraction. The complex value of the third-order susceptibility enhancement results in a sign change of n2 for the effective composite material relative to the pure BDPAS film. This complex nature of the enhancement and the tunability of the nanoantenna resonance allow for engineering the effective nonlinear response of the composite film.

We present femtosecond pump-probe measurements of the nondegenerate (1960$\,$nm excitation and 1176--1326$\,$nm probe) two-photon absorption spectra of 8 $\,$nm GaAs/12$\,$nm Al$_{0.32}$Ga$_{0.68}$As quantum well waveguides. Experiments were performed with light pulses co-polarized normal and tangential to the quantum well plane. The results are compared to perturbative calculations of transition rates between states determined by the $\mathbf{k}\cdot\mathbf{p}$ method with an 8 or 14 band basis. We find excellent agreement between theory and experiment for normal polarization, then use the model to support predictions of orders-of-magnitude enhancement of nondegenerate two-photon absorption as one constituent photon energy nears an intersubband resonance., 13 pages, 8 figures

International audience; New derivatives involving the photochromic 2H-benzo[h]chromene moieties covalently linked to the 2,7-bis(carbazolyl)fluorene-derived two-photon absorbing moiety were designed to enable the possibility of resonance energy transfer from the fluorene donor to the photochromic acceptor. The longest wavelength absorption of the photochromic acceptors overlaps with the fluorescence band of the two-photon absorbing donor and the distance between the both moieties is about 5–7 Å. Rapid coloration of colorless solutions was observed upon one- and two-photon absorption.

Two-photon absorption spectra for a range of bis(acceptor)-substituted bis(dibutoxythienyl)ethene and bis(N-hexylpyrrolyl)ethene chromophores have been recorded using Z-scan and white-light-continuum pump-probe techniques. All the chromophores studied show strong near-infrared two-photon absorption with cross sections in the range of 2400-5900 GM (1 GM = 1 × 10-50 cm 4 s/photon) at photon wavelengths between 1.0 and 1.3 μm; cross sections as high as 10000 GM can be accessed close to the one-photon absorption edge. Quantum-chemical calculations reproduce the experimentally observed variations of the two-photon properties with the chemical structure. © 2007 American Chemical Society.

Three new dipolar chromophores based on a diaklyaminophenyl donor, a pyrrole auxiliary donor, a thiazole auxiliary acceptor, and strong heterocyclic acceptors have been synthesized. For one of these compounds we have measured a very large non-degenerate two-photon cross section of ca. 1500 GM in the near-IR telecommunications range using a pump-probe technique. Calculations indicate the cross section for degenerate two-photon absorption is likely to be ca. 60% of this value.