Ab initio Molecular Dynamics Simulations of the Structural Response of Solids to Ultrashort Laser and XUV Pulses

The theoretical model and underlying physics described in this thesis are about the interaction of femtosecond-laser and XUV pulses with solids. The key to understand the basics of such interaction is to study the structural response of the materials after laser interaction. Depending on the laser characteristics, laser-solid interaction can result in a wide range of structural responses such as solid-solid phase transitions, vacuum phonon squeezing, ultrafast melting, generation of coherent phonons, etc. During my research work, I have modeled the systems irradiated by low-, medium- and high-laser intensities, and studied different types of structural dynamics of solids at various laser fluences.

Necrosis response to photodynamic therapy using light pulses in the femtosecond regime

One of the clinical limitations of the photodynamic therapy (PDT) is the reduced light penetration into biological tissues. Pulsed lasers may present advantages concerning photodynamic response when compared to continuous wave (CW) lasers operating under the same average power conditions. The aim of this study was to investigate PDT-induced response when using femtosecond laser (FSL) and a first-generation photosensitizer (Photogem) to evaluate the induced depth of necrosis. The in vitro photodegradation of the sensitizer was monitored during illumination either with CWor an FSL as an indirect measurement of the PDT response. Healthy liver of Wistar rats was used to evaluate the tissue response. The photosensitizer was endovenously injected and 30 min after, an energy dose of 150 Jcm-2 was delivered to the liver surface. We observed that the photodegradation rate evaluated via fluorescence spectroscopy was higher for the FSL illumination. The FSL-PDT produced a necrosis nearly twice as deep when compared to the CW-PDT. An increase of the tissue temperature during the application was measured and was not higher than 2.5 °C for the CW laser and not higher than 4.5 °C for the pulsed laser. FSL should be considered as an alternative in PDT applications for improving the results in the treatment of bulky tumors where higher light penetration is required.

Antisymmetric distribution of permanent refractive index change in β-BaB2O4 crystal under exposure of femtosecond pulses

We have observed unusual asymmetrical refractive index change as a result of femtosecond laser inscription in a crystal without center of inversion. Profile of the refractive index change exhibits sign turn within the domain of femtosecond pulse exposure. © Owned by the authors, published by EDP Sciences, 2013.

Differences in the early biomechanical effects of hyperopic and myopic laser in situ keratomileusis

PURPOSE: To compare changes in corneal hysteresis (CH) and the corneal resistance factor (CRF) in myopic and hyperopic laser in situ keratomileusis (LASIK) and evaluate their relationship to the number of photoablative pulses delivered, a surrogate for ablation volume. SETTING: Cleveland Clinic Cole Eye Institute, Cleveland, Ohio, USA. METHODS: Preoperative and 1-week postoperative Ocular Response Analyzer measurements in eyes that had femtosecond-assisted LASIK were studied retrospectively. Changes in CH and CRF were compared and tested for correlation with the number of excimer laser pulses. RESULTS: Thirteen myopic eyes and 11 hyperopic eyes were evaluated. Preoperative corneal thickness, CH, CRF, programmed correction magnitude, flap thickness, and total number of fixed spotsize photoablative pulses were similar in the 2 groups (P>.1). Decreases in CH and CRF were greater after myopic LASIK than after hyperopic LASIK (P<.005), and changes in CRF were correlated with the number of excimer laser pulses in the myopic group only (r = -0.63, P = .02). Regardless of ablation profile, changes in CH were more strongly correlated with preoperative CH values than with attempted ablation volume. CONCLUSIONS: With comparable flap thickness and attempted ablation volumes, myopic photoablation profiles were associated with greater decreases in CRF and CH than hyperopic profiles. Results indicate that preoperative corneal biomechanical status, ablation volume, and the spatial distribution of ablation are important factors that affect corneal resistance and viscous dissipative properties differently. Preferential tissue removal in the natively thicker paracentral cornea in hyperopia may partially account for the rarity of ectasia after hyperopic LASIK.

Internal structure of the nanogratings generated inside bulk fused sílica by ultrafast laser direct writing

The aim of the present work was to characterize the internal structure of nanogratings generated inside bulk fused silica by ultrafast laser processing and to study the influence of diluted hydrofluoric acid etching on their structure. The nanogratings were inscribed at a depth of 100 mu m within fused silica wafers by a direct writing method, using 1030 nm radiation wavelength and the following processing parameters: E = 5 mu J, tau = 560 fs, f = 10 kHz, and v = 100 mu m/s. The results achieved show that the laser-affected regions are elongated ellipsoids with a typical major diameter of about 30 mu m and a minor diameter of about 6 mu m. The nanogratings within these regions are composed of alternating nanoplanes of damaged and undamaged material, with an average periodicity of 351 +/- 21 nm. The damaged nanoplanes contain nanopores randomly dispersed in a material containing a large density of defects. These nanopores present a roughly bimodal size distribution with average dimensions for each class of pores 65 +/- 20 x 16 +/- 8 x 69 +/- 16 nm(3) and 367 +/- 239 x 16 +/- 8 x 360 +/- 194 nm(3), respectively. The number and size of the nanopores increases drastically when an hydrofluoric acid treatment is performed, leading to the coalescence of these voids into large planar discontinuities parallel to the nanoplanes. The preferential etching of the damaged material by the hydrofluoric acid solution, which is responsible for the pores growth and coalescence, confirms its high defect density. (C) 2014 AIP Publishing LLC.

Control and femtosecond time-resolved imaging of torsion in a chiral molecule

We study how the combination of long and short laser pulses can be used to induce torsion in an axially chiral biphenyl derivative (3,5-difluoro-3 ,5 -dibromo-4 -cyanobiphenyl). A long, with respect to the molecular rotational periods, elliptically polarized laser pulse produces 3D alignment of the molecules, and a linearly polarized short pulse initiates torsion about the stereogenic axis. The torsional motion is monitored in real-time by measuring the dihedral angle using femtosecond time-resolved Coulomb explosion imaging. Within the first 4 picoseconds (ps), torsion occurs with a period of 1.25 ps and an amplitude of 3◦ in excellent agreement with theoretical calculations. At larger times, the quantum states of the molecules describing the torsional motion dephase and an almost isotropic distribution of the dihedral angle is measured.We demonstrate an original application of covariance analysis of two-dimensional ion images to reveal strong correlations between specific ejected ionic fragments from Coulomb explosion. This technique strengthens our interpretation of the experimental data

Femtosecond probing of sodium cluster ion Na_n ^+ fragmentation

We report on the first femtosecond time-resolved experiments in cluster physics. The photofragmentation dynamics of small sodium cluster ions Na_n ^+ have been studied with pump-probe techniques. Ultrashort laser pulses of 60-fs duration are employed to photoionize the sodium clusters and to probe the photofragments. We find that the ejection of neutral dimer Na_2 and, observed for the first time, neutral trimer Na_3 photofragments occur on ultrashort time scales of 2.5 and 0.4 ps, respectively. This and the absence of cluster heating reveals that direct photoinduced fragmentation processes are important at short times rather than the statistical unimolecular decay.

Femtosecond pump-probe study of the spreading and recurrence of a vibrational wave packet in Na_2

The motion of a vibrational wave packet in the bound A(^1 \summe^+_u) electronic state of the sodium dimer is detected in a femtosecond pump/probe molecular beam experiment. For short times harmonic motion is seen in the total ion yield of Na^+_2 as a function of delay time between the two laser pulses. The spreading of the wave packet results in the loss of the periodic variation of the ion signal. For longer delay times (47 ps) the wave packet regains its initial form which is reflected in the revival structure of the Na^+_2 signal. Time-dependent quantum calculations reproduce the measured effects.

Femtosecond dynamics of molecules and clusters

The real-time dynamics of multiphoton ionization and fragmentation of molecules - Na_2 , Na_3 - and clusters - Na_n, Hg_n - has been studied in molecular beam experiments employing ion and electron spectroscopy together with femtosecond pump-probe techniques. Experiments with Na_2 and Na_3 reveal unexpected features of the dynamics of the absorption of several photons as seen in the one- and three dimensional vibrational wave packet motion in different potential surfaces and in high laser fields. Cluster size dependent studies of physical properties such as absorption resonances, lifetimes and decay channels have been performed using tunable femtosecond light pulses in resonance enhanced multiphoton ionization (REMPI) of the cluster size under investigation. This method failed in ns-laser experiments due to the ultrafast decay of the studied cluster. For Na_n, cluster we find that for cluster sizes n \le 21 molecular excitations and properties prevail over collective excitations of plasmon-like resonances. In the case of Hg_n cluster prompt formation of singly and doubly charged cluster are observed up to n \approx 60. The transient multiphoton ionization spectra show a 'short' time wave packet dynamics, which is identical for singly and doubly charged mercury clusters while the 'long' time fragmentation dynamics is different.

Femtosecond pulse shaping using differential evolutionary algorithm and wavelet operators

Evolutionary meta-algorithms for pulse shaping of broadband femtosecond duration laser pulses are proposed. The genetic algorithm searching the evolutionary landscape for desired pulse shapes consists of a population of waveforms (genes), each made from two concatenated vectors, specifying phases and magnitudes, respectively, over a range of frequencies. Frequency domain operators such as mutation, two-point crossover average crossover, polynomial phase mutation, creep and three-point smoothing as well as a time-domain crossover are combined to produce fitter offsprings at each iteration step. The algorithm applies roulette wheel selection; elitists and linear fitness scaling to the gene population. A differential evolution (DE) operator that provides a source of directed mutation and new wavelet operators are proposed. Using properly tuned parameters for DE, the meta-algorithm is used to solve a waveform matching problem. Tuning allows either a greedy directed search near the best known solution or a robust search across the entire parameter space.

Laser microstructuring of azopolymers via surface relief gratings: controlling hydrophobicity

In this paper the large-scale mass transport mechanism is used to microstructure azopolymeric films, aiming at controllable hydrophobic surfaces. Using an Ar(+) laser with intensity of 70 mW/cm(2), we produced egg-crate-like surfaces with periods from 1.0 to 3.5 mu m that present distinct wetting properties. The static contact angle of water was measured on the microstructured surfaces, and the results revealed an increase of approximately 9 degrees for a surface pattern period of 2 mu m. Our results indicate the use of the microstructuring method described here for the fabrication of devices with controllable hydrophobicity.

MEH-PPV photobleaching control by femtosecond pulse shaping

In the work reported here we were able to control the photobleaching of poly[2-methoxy-5-(2`-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV), excited by two-photon absorption, using femtosecond pulse shaping. By applying a cosine-like spectral phase mask, we observe a reduction of three times in the photobleaching rate, while the fluorescence intensity decreases by 20%, in comparison to the values obtained with a Fourier-transform-limited pulse. These results demonstrate an interesting trade-off between photobleaching rate and nonlinear fluorescence intensity. The possible mechanism behind this process is discussed in terms of the pulse spectral profile and the absorbance band of MEH-PPV. (C) 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Laser microstructuring for fabricating superhydrophobic polymeric surfaces

In this paper we show the fabrication of hydrophobic polymeric surfaces through laser microstructuring. By using 70-ps pulses from a Q-switched and mode-locked Nd:YAG laser at 532 nm, we were able to produce grooves with different width and separation, resulting in square-shaped pillar patterns. We investigate the dependence of the morphology on the surface static contact angle for water, showing that it is in agreement with the Cassie-Baxter model. We demonstrate the fabrication of a superhydrophobic polymeric surface, presenting a water contact angle of 157 degrees. The surface structuring method presented here seems to be an interesting option to control the wetting properties of polymeric surfaces. (C) 2010 Elsevier B.V. All rights reserved.

Production of defects in ZBLAN, ZBLAN : Tm3+ and ZBLAN : Cr3+ glasses by ultra-short pulses laser interaction

In this work we have studied pure and thulium- and chromium-doped ZBLAN glasses irradiated by ultra-short laser pulses. A Ti:sapphire CPA system was used, producing a 500 Hz train of pulses, centered at 830 nm, with 375 mu J of energy and 50 fs of duration (FWHM). The beam was focused by a 20 Him lens, producing a converging beam with a waist of 12 pin. The absorption spectra before and after laser irradiation were obtained showing production of color centers in pure, thulium-doped and chromium-doped ZBLAN glasses. A damage threshold of 9.56 TW/cm(2) was determined for ZBLAN. (C) 2007 Elsevier Ltd. All rights reserved.

Effect of pulse repetition rate and number of pulses in the analysis of polypropylene and high density polyethylene by nanosecond infrared laser induced breakdown spectroscopy

Pulse repetition rates and the number of laser pulses are among the most important parameters that do affect the analysis of solid materials by laser induced breakdown spectroscopy, and the knowledge of their effects is of fundamental importance for suggesting analytical strategies when dealing with laser ablation processes of polymers. In this contribution, the influence of these parameters in the ablated mass and in the features of craters was evaluated in polypropylene and high density polyethylene plates containing pigment-based PbCrO4. Surface characterization and craters profile were carried out by perfilometry and scanning electron microscopy. Area, volume and profile of craters were obtained using Taylor Map software. A laser induced breakdown spectroscopy system consisted of a Q-Switched Nd:YAG laser (1064 nm, 5 ns) and an Echelle spectrometer equipped with ICCD detector were used. The evaluated operating conditions consisted of 10, 25 and 50 laser pulses at 1, 5 and 10 Hz, 250 mJ/pulse (85 J cm(-2)), 2 mu s delay time and 6 mu s integration time gate. Differences in the topographical features among craters of both polymers were observed. The decrease in the repetition rate resulted in irregular craters and formation of edges, especially in polypropylene sample. The differences in the topographical features and ablated masses were attributed to the influence of the degree of crystallinity, crystalline melting temperature and glass transition temperature in the ablation process of the high density polyethylene and polypropylene. It was also observed that the intensities of chromium and lead emission signals obtained at 10 Hz were two times higher than at 5 Hz by keeping the number of laser pulses constant. (C) 2011 Elsevier B. V. All rights reserved.