Tuning the Photophysical Properties of Aza-BODIPYs in the Near-Infrared Region by Introducing Electron-Donating Thiophene Substituents.

This study presents the synthesis, the spectroscopic and electrochemical properties of new bis- and tetra-substituted azaboron-dipyrromethene (aza-BODIPY) dyes substituted by different electron donating groups connected to the aza-BODIPY core through a thiophene unit. In line with theoretical calculations, experimental measurements point out the positive impact of the thiophene group that behave as a secondary donor group leading to an enhancement of the intramolecular charge transfer process in comparison to previously reported aza-BODIPY dyes. This heterocycle has also been found to tune the oxidative potential and to stabilize the electro-generated species.

Femtosecond Spectroscopy and Nonlinear Optical Properties of aza-BODIPY Derivatives in Solution.

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  m2 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.

Improving Orientation, Packing Density, and Molecular Arrangement in Self-Assembled Monolayers of Bianchoring Ferrocene-Triazole Derivatives by "Click" Chemistry.

This work describes the self-assembled monolayers (SAMs) of two ferrocene derivatives with two anchoring groups (at the bottom and at the top of the SAM) deposited on ultraflat template-stripped gold substrates by cyclic voltammetry and analyzed by complementary surface characterization techniques. The SAM of each molecule is deposited by three different protocols: direct deposition (one step), click reaction on the surface (two steps), and reverse click reaction on the surface (two steps). The SAM structure is well studied to determine the SAM orientation, SAM arrangement, and ferrocene position within the SAM. Electron transfer kinetics have also been studied, which agree with the quality of each SAM. With the help of two anchoring groups and click-chemistry active functional groups, we have shown that the two molecules can be deposited by controlling the position of ferrocene at either end. We further investigated the involvement of the triazole five-membered ring in the electron transfer mechanism. We have found that a carbon spacer between ferrocene and triazole improves the SAM packing. This study enhances the understanding of tethering thiol and thiol acetate anchoring groups on gold by a controlled orientation, which may help in the development of functional molecular devices requiring two anchoring groups.

Benzothiadiazole-Substituted Aza-BODIPY Dyes: Two-Photon Absorption Enhancement for Improved Optical Limiting Performances in the Short-Wave IR Range.

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.

Plasmonic Nanocomposites Based on Silver Nanocube-Polymer Blends Displaying Nearly Perfect Absorption in the UV Region.

Plasmonic nanocomposites based on well-dispersed silver nanocubes in poly(vinylpyrrolidone) are presented that are solution-processed into layers of varying volume fractions of nanocubes. We show that the high-energy modes of the nanocubes are almost insensitive to plasmonic coupling within the nanocube assemblies, leading to a linear increase in light absorption in the UV region with the nanocube densities. Concerning the main dipolar resonance mode at 450 nm, it is strongly affected by the formation of these assemblies, leading to an increased absorption in the UV region as well as a large absorption band in the visible region. Simulations of the optical response of the nanocube assemblies as a function of nanocube spacing and electric field polarization reveal that optical features in the visible region are due to intercube couplings at short intercube distances and parallel electric field orientation. In contrast, the additional plasmonic band in the UV region has its origin in residual dipolar oscillations of the nanocubes in combination with weak dipolar coupling for both parallel and transversal field polarizations. The combination of these effects leads to an enlarged absorption band in the UV region with nearly perfect light absorption of 98.8% at a high silver volume fraction of 8% that is accompanied by a very weak specular reflection of only 0.28%. Although such perfect absorption is usually observed only when nanocubes are assembled on a gold surface, nearly perfect absorption herein is achieved on a large palette of substrates including glass, plastic, and cheap metals such as aluminum, making it a promising approach for solution-processed robust and cheap quasi-perfect absorption coatings.

Metamaterial filters at optical-infrared frequencies.

We propose two distinctive designs of metamaterials demonstrating filtering functions in the visible and near infrared region. Since the emissivity is related to the absorption of a material, these filters would then offer a high emissivity in the visible and near infrared, and a low one beyond those wavelengths. Usually, such a system find their applications in the thermo-photovoltaics field as it can find as well a particular interest in optoelectronics, especially for optical detection. Numerical analysis has been performed on common metamaterial designs: a perforated metallic plate and a metallic cross grating. Through all these structures, we have demonstrated the various physical phenomena contributing to a reduction in the reflectivity in the optical and near infrared region. By showing realistic geometric parameters, the structures were not only designed to demonstrate an optical filtering function but were also meant to be feasible on large surfaces by lithographic methods such as micro contact printing or nano-imprint lithography.

Flat-top and patterned-topped cone gratings for visible and mid-infrared antireflective properties.

Achieving a broadband antireflection property from material surfaces is one of the highest priorities for those who want to improve the efficiency of solar cells or the sensitivity of photo-detectors. To lower the reflectance of a surface, we are concerned with the study of the optical response of flat-top and patterned-topped cone shaped silicon gratings, based on previous work exploring pyramid gratings. Through rigorous numerical methods such as Finite Different Time Domain, we first designed several flat-top structures that theoretically demonstrate an antireflective character within the middle infrared region. From the opto-geometrical parameters such as period, depth and shape of the pattern determined by numerical analysis, these structures have been fabricated using controlled slope plasma etching processes. In order to extend the antireflective properties up to the visible wavelengths, patterned-topped cones have been fabricated as well. Afterwards, optical characterizations of several samples were carried out. Thus, the performances of the flat-top and patterned-topped cones have been compared in the visible and mid infrared range.

Excited state absorption: a key phenomenon for the improvement of biphotonic based optical limiting at telecommunication wavelengths.

Spectroscopic properties, two-photon absorption (TPA) and excited state absorption (ESA), of two organic cyanine dyes and of a ruthenium based organometallic cyanine are compared in order to rationalize their similar ns-optical power limiting (OPL) efficiency in the telecommunication wavelength range. The TPA contribution to the ns-OPL behavior is higher for both organic cyanines, while the main process is a TPA-induced ESA in the case of the organometallic system, in which the ruthenium induces a broadening of the NIR-ESA band and resulting in a strong spectral overlap between TPA and ESA spectra.

Sand-castle biperiodic pattern for spectral and angular broadening of antireflective properties.

This Letter deals with the antireflective properties of top-patterned pyramids, looking like sand castles, bi-periodically repeated on a silicon surface. It is demonstrated numerically that such an original pattern allows a dramatic spectral and angular broadening of the antireflective efficiency. Design examples are given for wavelengths ranging from 0.5 microm to 5 microm and incidence angles of 30 degrees and 45 degrees. Applications of such antireflective surfaces on photodetectors and solar cells are soon expected.

Near-infrared active polarimetric and multispectral laboratory demonstrator for target detection.

We report on the design and exploitation of a real-field laboratory demonstrator combining active polarimetric and multispectral functions. Its building blocks, including a multiwavelength pulsed optical parametric oscillator at the emission side and a hyperspectral imager with polarimetric capability at the reception side, are described. The results obtained with this demonstrator are illustrated on some examples and discussed. In particular it is found that good detection performances rely on joint use of intensity and polarimetric images, with these images exhibiting complementary signatures in most cases.

Optical response of heterogeneous polymer layers containing silver nanostructures.

This work is focused on the study of the optical properties of silver nanostructures embedded in a polymer host matrix. The introduction of silver nanostructures in polymer thin films is assumed to result in layers having adaptable optical properties. Thin film layers with inclusions of differently shaped nanoparticles, such as nanospheres and nanoprisms, and of different sizes, are optically characterized. The nanoparticles are produced by a simple chemical synthesis at room temperature in water. The plasmonic resonance peaks of the different colloidal solutions range from 390 to 1300 nm. The non-absorbing, transparent polymer matrix poly(vinylpyrrolidone) (PVP) was chosen because of its suitable optical and chemical properties. The optical studies of the layers include spectrophotometry and spectroscopic ellipsometry measurements, which provide information about the reflection, transmission, absorption of the material as well as the complex optical indices, n and k. Finite difference time domain simulations of nanoparticles in thin film layers allow the visualization of the nanoparticle interactions or the electric field enhancement on and around the nanoparticles to complete the optical characterization. A simple analysis method is proposed to obtain the complex refractive index of nanospheres and nanoprisms in a polymer matrix.

Optical and electrical properties between 0.4 and 12 microm for Sn-doped In2O3 films by pulsed laser deposition and cathode sputtering.

Optical properties of Sn-doped In(2)O(3) (ITO) have been studied in the optical range of 0.4-12 microm. A deposition has been made on BK7 glass, magnesium fluoride, sapphire, and zinc sulfide substrates. The layers have been characterized by their optical properties, DC electrical sheet resistivity, and Hall mobility. Sheet resistivity lies in the range of 6.8-318 Omega/sq for thicknesses between 16 and 280 nm. The best carrier mobility is obtained on BK7 and sapphire substrates, up to approximately 50 cm(2)/V s. The material shows good infrared transparency in the 3-5 microm range on magnesium fluoride and 0.4-4 microm on sapphire, and it is usable for practical applications up to 12 microm on zinc sulfide. Simulations have been carried out for optical indices and spectra calculations. The Drude model has been used to exploit the results in either direction: from electrical measured data to the simulation of optical spectra and indices, and from measured optical spectra to simulated optical indices and electrical parameters (mobility, carrier density). Hall mobility is considered a worthy and convenient material quality criteria for materials aimed at optics.