Laser induced periodic surface structuring on Si by temporal shaped femtosecond pulses.

We investigated the effect of temporal shaped femtosecond pulses on silicon laser micromachining. By using sinusoidal spectral phases, pulse trains composed of sub-pulses with distinct temporal separations were generated and applied to the silicon surface to produce Laser Induced Periodic Surface Structures (LIPSS). The LIPSS obtained with different sub-pulse separation were analyzed by comparing the intensity of the two-dimensional fast Fourier Transform (2D-FFT) of the AFM images of the ripples (LIPSS). It was observed that LIPSS amplitude is more emphasized for the pulse train with sub-pulses separation of 128 fs, even when compared with the Fourier transform limited pulse. By estimating the carrier density achieved at the end of each pulse train, we have been able to interpret our results with the Sipe-Drude model, that predicts that LIPSS efficacy is higher for a specific induced carrier density. Hence, our results indicate that temporal shaping of the excitation pulse, performed by spectral phase modulation, can be explored in fs-laser microstructuring.

Direct laser writing by two-photon polymerization as a tool for developing microenvironments for evaluation of bacterial growth.

Monitoring bacteria growth and motion in environments is fundamental to understand, for instance, how they proliferate and contaminate organism. Therefore, techniques to fabricate microenvironments for in situ and in vivo studies are interesting for that purpose. In this work we used two-photon polymerization to fabricate microenvironments and, as a proof of principle, we demonstrated the development of the bacteria ATCC 25922 Escherichia coli (E. coli) into the microstructure surroundings. Two varieties of polymeric microenvironments are presented: (i) a microenvironment doped at specific site with ciprofloxacin, an antibiotic typically used in the treatment of diseases caused by E. coli and (ii) micro-fences, which serve as traps for bacteria. These microenvironments, fabricated by two-photon polymerization, may be a potential platform for drug delivery system, by promoting or inhibiting the growth of bacteria in specific biological or synthetic sites.

Effect of interaction with micelles on the excited-state optical properties of zinc porphyrins and J-aggregates formation.

This work reports on the photophysical properties of zinc porphyrins meso-tetrakis methylpyridiniumyl (Zn(2+)TMPyP) and meso-tetrakis sulfonatophenyl (Zn(2+)TPPS) in homogeneous aqueous solutions and in the presence of sodium dodecyl sulfate (SDS) and cetyltrimethyl ammonium bromide (CTAB) micelles. The excited-state dynamic was investigated with the Z-scan technique, UV-Vis absorption, and fluorescence spectroscopy. Photophysical parameters were obtained by analyzing the experimental data with a conventional five-energy-level diagram. The interaction of the charged side porphyrin groups with oppositely charged surfactants can reduce the electrostatic repulsion between porphyrin molecules leading to aggregation, which affected the porphyrin characteristics such as absorption cross-sections, lifetimes and quantum yields. The interaction between anionic ZnTPPS with cationic CTAB micelles induced the formation of porphyrin J-aggregates, while this effect was not observed in the interaction of ZnTMPyP with SDS micelles. This difference is, probably, due to the difference in electrostatic repulsion between the porphyrin molecules. The insights obtained by these results are important for the understanding of the photophysical behavior of porphyrins, regarding potential applications in pharmacokinetics as encapsulation of photosensitizer for drug delivery systems and in its interaction with cellular membrane.

Effect of solvent-induced coil to helix conformational change on the two-photon absorption spectrum of poly(3,6-phenanthrene).

This paper investigates the effect of solvent-induced conformational changes of poly(3,6-phenanthrene) on their two-photon absorption (2PA). Such effect was studied employing the wavelength-tunable femtosecond Z-scan technique and modeled using the sum-over-essential states approach. We observed a strong reduction of the 2PA cross-section when the sample was prepared in hexane (poor solvent) in comparison to chloroform (good solvent), which is related to the conformation adopted by the polymer in each case. In chloroform it adopts a random coil conformation, as opposed to the one-handed helix conformation in hexane. Our results pointed out that the coil to helix conformation change decreases the degree of molecular planarity of the polymer π-conjugated backbone, which is primarily responsible for their optical nonlinearity, contributing to diminishing the effective transition dipole moments and, consequently, the 2PA cross-section. Moreover, by studying the nonlinear response with different light polarization, we showed that, although the solvent-induced conformational change does not alter the molecular symmetry of the polymer, it modifies considerably the direction of the transition dipole moments between the excited states.

Polarization effect on the two-photon absorption of a chiral compound.

In this report, we investigate the polarization effect (linear, elliptical and circular) on the two-photon absorption (2PA) properties of a chiral compound based in azoaromatic moieties using the femtosecond Z-scan technique with low repetition rate and low pulse energy. We observed a strong 2PA modulation between 800 nm and 960 nm as a function the polarization changes from linear through elliptical to circular. Such results were interpreted employing the sum-over-essential states approach, which allowed us to model the 2PA circular-linear dichroism effect and to identifier the overlapping of the excited electronic states responsible by the 2PA allowed band.

Generation of copper nanoparticles induced by fs-laser irradiation in borosilicate glass.

Glasses containing metallic nanoparticles are promising materials for technological applications in optics and photonics. Although several methods are available to generate nanoparticles in glass, only femtosecond lasers allow controlling it three-dimensionally. In this direction, the present work investigates the generation of copper nanoparticles on the surface and in the bulk of a borosilicate glass by fs-laser irradiation. We verified the formation of copper nanoparticles, after heat treatment, by UV-Vis absorption, transmission electron microscopy and electron diffraction. A preferential growth of copper nanoparticles was observed in the bottom of the irradiated region, which was attributed to self-focusing in the glass.

Temperature effect on the two-photon absorption spectrum of all-trans-ß-carotene.

In this report, we investigate the influence of temperature on the two-photon absorption (2PA) spectrum of all-trans-ß-carotene using the femtosecond white-light-continuum Z-scan technique. We observed that the 2PA cross-section decreases quadratically with the temperature. Such effect was modeled using a three-energy-level diagram within the sum-over-essential states approach, assuming temperature dependencies to the transition dipole moment and refractive index of the solvent. The results show that the transition dipole moments from ground to excited state and between the excited states, which governed the two-photon matrix element, have distinct behaviors with the temperature. The first one presents a quadratic dependence, while the second exhibits a linear dependence. Such effects were attributed mainly to the trans→cis thermal interconversion process, which decreases the effective conjugation length, contributing to diminishing the transition dipole moments and, consequently, the 2PA cross-section.

Femtosecond laser induced synthesis of Au nanoparticles mediated by chitosan.

This paper reports the synthesis of Au nanoparticles by 30-fs pulses irradiation of a sample containing HAuCl4 and chitosan, a biopolymer used as reducing agent and stabilizer. We observed that it is a multi-photon induced process, with a threshold irradiance of 3.8 × 10(11) W/cm2 at 790 nm. By transmission electron microscopy we observed nanoparticles from 8 to 50 nm with distinct shapes. Infrared spectroscopy indicated that the reduction of gold and consequent production of nanoparticles is related to the fs-pulse induced oxidation of hydroxyl to carbonyl groups in chitosan.

Linear and nonlinear optical properties of the thiophene/phenylene-based oligomer and polymer.

In this article, we investigate the linear and nonlinear optical properties of the thiophene/phenylene-based oligomer (SL128G) and polymer (FSE59) chemically modified with alquilic chains, which allow greater solubility and provide new optical properties. These compounds present a strong absorption in the UV-visible region, providing a wide transparence window in visible-IR, ideal for applications in nonlinear optics. Employing the Z-scan technique with femtosecond pulses, we show that these compounds exhibit considerable two-photon absorption (2PA), with two 2PA allowed states located at 650 and 800 nm for SL128G and 780 and 920 nm for FSE59. Moreover, we observe the resonance enhancement effect as the excitation wavelength approaches the lowest one-photon-allowed state. By modeling the 2PA spectra considering a four-energy-level diagram within of the sum-over-essential states approach, we obtained the spectroscopic parameters of the electronic transitions to low-energy singlet excited states. Additionally, photoluminescence excited by femtosecond and picosecond pulses were performed to confirm the order of the multiphoton process and estimate the fluorescence lifetime, respectively.

Third-order nonlinear spectra and optical limiting of lead oxifluoroborate glasses.

We have determined two-photon absorption and nonlinear refraction spectra of the 50BO(1.5) - (50-x)PbF(2) - xPbO glasses (with x = 25, 35, 50 cationic %) at the range of the 470 and 1550 nm. The replacement of fluor atoms by oxygen leads to an increase in the third-order susceptibility, due to the formation of non-bridging oxygens (NBO). The nonlinear index of refraction is one order of magnitude higher than the one for fused silica, and it increases almost twice for the sample with x = 50. This sample has also shown promising features for all-optical switching as well as for optical limiting.

Experimental and theoretical study of two-photon absorption in nitrofuran derivatives: Promising compounds for photochemotherapy.

We report experimental and theoretical studies of the two-photon absorption spectrum of two nitrofuran derivatives: nitrofurantoine, (1-(5-nitro-2-furfurilideneamine)-hidantoine) and quinifuryl, 2-(5(')-nitro-2(')-furanyl)ethenyl-4-{N-[4(')-(N,N-diethylamino)-1(')-methylbutyl]carbamoyl} quinoline. Both molecules are representative of a family of 5-nitrofuran-ethenyl-quinoline drugs that have been demonstrated to display high toxicity to various species of transformed cells in the dark. We determine the two-photon absorption cross-section for both compounds, from 560 to 880 nm, which present peak values of 64 GM for quinifuryl and 20 GM for nitrofurantoine (1 GM = 1×10(-50)cm(4).s.photon(-1)). Besides, theoretical calculations employing the linear and quadratic response functions were carried out at the density functional theory level to aid the interpretations of the experimental results. The theoretical results yielded oscillator strengths, two-photon transition probabilities, and transition energies, which are in good agreement with the experimental data. A higher number of allowed electronic transitions was identified for quinifuryl in comparison to nitrofurantoine by the theoretical calculations. Due to the planar structure of both compounds, the differences in the two-photon absorption cross-section values are a consequence of their distinct conjugation lengths.

Nonlinear spectra of ZnO: reverse saturable, two- and three-photon absorption.

We present a broadband (460 - 980 nm) analysis of the nonlinear absorption processes in bulk ZnO, a large-bandgap material with potential blue-to-UV photonic device applications. Using an optical parametric amplifier we generated tunable 1-kHz repetition rate laser pulses and employed the Z-scan technique to investigate the nonlinear absorption spectrum of ZnO. For excitation wavelengths below 500 nm, we observed reverse saturable absorption due to one-photon excitation of the sample, agreeing with rate-equation modeling. Two- and three-photon absorption were observed from 540 to 980 nm. We also determined the spectral regions exhibiting mixture of nonlinear absorption mechanisms, which were confirmed by photoluminescence measurements.

Degenerate two-photon absorption in all-trans retinal: nonlinear spectrum and theoretical calculations.

In this work we investigate the degenerate two-photon absorption spectrum of all-trans retinal in ethanol employing the Z-scan technique with femtosecond pulses. The two-photon absorption (2PA) spectrum presents a monotonous increase as the excitation wavelength approaches the one-photon absorption band and a peak at 790 nm. We attribute the 2PA band to the mixing of states (1)B(u)(+)-like and |S(1)>, which are strongly allowed by one- and two-photon, respectively. We modeled the 2PA spectrum by using the sum-over-states approach and obtained spectroscopic parameters of the electronic transitions to |S(1)>, |S(2)> ("(1)B(u)(+)"), |S(3)>, and |S(4)> singlet-excited states. The results were compared with theoretical predictions of one- and two-photon transition calculations using the response functions formalism within the density functional theory framework with the aid of the CAM-B3LYP functional.

Two-photon polymerization for fabricating structures containing the biopolymer chitosan.

Two-photon polymerization is a powerful tool for fabricating three-dimensional micro/nano structures for applications ranging from nanophotonics to biology. To tailor such structure for specific purposes it is often important to dope them. In this paper we report on the fabrication of structures, with nanometric surface features (resolution of approximately 700 nm), using two-photon polymerization of an acrylic resin doped with the biocompatible polymer chitosan using a guest-host scheme. The fluorescence background in the Raman spectrum indicates the presence of chitosan throughout the structure. Mechanical characterization reveals that chitosan does not affect the mechanical properties of the host acrylic resin and, consequently, the structures exhibit excellent integrity. The approach presented in this work can be used in the fabrication of micro- and nanostructures containing biopolymers for biomedical applications.

Control of two-photon absorption in organic compounds by pulse shaping: spectral dependence.

In this work, we investigate the control of the two-photon absorption process of a series of organic compounds via spectral phase modulation of the excitation pulse. We analyzed the effect of the pulse central wavelength on the control of the two-photon absorption process for each compound. Depending on the molecules' two-photon absorption position relative to the excitation pulse wavelength, different levels of coherent control were observed. By simulating the two-photon transition probability in molecular systems, taking into account the band structure and its positions, we could explain the experimental results trends. We observed that the intrapulse coherent interference plays an important role in the nonlinear process control besides just the pulse intensity modulation.

Theoretical study of one- and two-photon absorption spectra of azoaromatic compounds.

In this study, the one- and two-photon absorption spectra of seven azoaromatic compounds (five pseudostilbenes-type and two aminoazobenzenes) were theoretically investigated using the density functional theory combined with the response functions formalism. The equilibrium molecular structure of each compound was obtained at three different levels of theory: Hartree-Fock, density functional theory (DFT), and Møller-Plesset 2. The effect of solvent on the equilibrium structure and the electronic transitions of the compounds were investigated using the polarizable continuum model. For the one-photon absorption, the allowed pi-->pi(*) transition energy showed to be dependent on the molecular structures and the effect of solvent, while the n-->pi(*) and pi-->pi(*)(n) transition energies exhibited only a slight dependence. An inversion between the bands corresponding to the pi-->pi(*) and n-->pi(*) states due to the effect of solvent was observed for the pseudostilbene-type compounds. To characterize the allowed two-photon absorption transitions for azoaromatic compounds, the response functions formalism combined with DFT using the hybrid B3LYP and PBE0 functionals and the long-range corrected CAM-B3LYP functional was employed. The theoretical results support the previous findings based on the three-state model. The model takes into account the ground and two electronic excited states and has already been used to describe and interpret the two-photon absorption spectrum of azoaromatic compounds. The highest energy two-photon allowed transition for the pseudostilbene-type compounds shows to be more effectively affected (approximately 20%) by the torsion of the molecular structure than the lowest allowed transition (approximately 10%). In order to elucidate the effect of the solvent on the two-photon absorption spectra, the lowest allowed two-photon transition (dipolar transition) for each compound was analyzed using a two-state approximation and the polarizable continuum model. The results obtained reveal that the effect of solvent increases drastically the two-photon cross-section of the dipolar transition of the pseudostilbene-type compounds. In general, the features of both one- and two-photon absorption spectra of the azoaromatic compounds are well reproduced by the theoretical calculations.

Resonant nonlinear absorption in Zn-phthalocyanines.

In this work, we investigate the nonlinear absorption dynamics of Zn phthalocyanine in dimethyl sulfoxide (DMSO). We used single pulse and pulse train Z-scan techniques to determine the dynamics and absorption cross-sections of singlet and triplet states at 532 nm. The excited singlet state absorption cross-section was determined to be 3.2 times higher than the ground state one, giving rise to reverse saturable absorption. We also observed that reverse saturable absorption occurs from the triplet state, after its population by intersystem crossing, whose characteristic time was determined to be 8.9 ns. The triplet state absorption cross-section determined is 2.6 times higher than the ground state one. In addition, we used the white light continuum Z-scan to evaluate the singlet excited state spectrum from 450 to 710 nm. The results show two well-defined regions, one above 600 nm, where reverse saturable absorption is predominant. Below 600 nm, we detected a strong saturable absorption. A three-energy-level diagram was used to explain the experimental results, leading to the excited state absorption cross-section determination from 450 nm up to 710 nm.

Femtosecond laser waveguide micromachining of PMMA films with azoaromatic chromophores.

We report on the femtosecond-laser micromachining of poly(methyl methacrylate) (PMMA) films doped with nonlinear azoaromatic chromophores: Disperse Red 1, Disperse Red 13 and Disperse Orange 3. We study the conditions for controlling chromophore degradation during the micromachining of PMMA doped with each chromophore. Furthermore, we successfully used fs-micromachining to fabricate optical waveguides within a bulk sample of PMMA doped with these azochromophores.

Two-photon absorption dependence on the temperature for azoaromatic compounds: effect of molecular conformation.

This work reports on the effect of temperature on the two-photon absorption cross section of azoaromatic chromophores. A linear decrease in the two-photon absorption cross section with the temperature was observed for several azochromophores. This process was characterized by introducing a two-photon absorption thermal coefficient (ddelta/dT), whose typical values are approximately 2GM/degrees C for all the azochromophores studied here. Such an effect was attributed to thermal induced molecular conformation changes, described by the sum-over-states model and semiempirical calculations, which affect the molecular dipole moments. The characterization of the phenomenon reported here for other nonlinear materials can help in the design of specific applications using two-photon absorption.

Excited state absorption spectrum of chlorophyll a obtained with white-light continuum.

The study of excited state properties of chlorophyll a is a subject of foremost interest, given that it plays important roles in biological process and has also been proposed for applications in photonics. This work reports on the excited state absorption spectrum of chlorophyll a solution from 460 to 700 nm, obtained through the white-light continuum Z-scan technique. Saturation of absorption was observed due to the ground state depletion, induced by the white-light continuum region that is resonant with the Q band of chlorophyll a. The authors also observed reverse saturation of absorption related to the excitation from the first excited state to a higher energy level for wavelengths below 640 nm. An energy-level diagram, based on the electronic states of chlorophyll a, was employed to interpret their results, revealing that more states than the ones related to the Q and B bands participate in the excited state absorption of this molecule.