Revealing the impact of strain in the optical properties of bubbles in monolayer MoSe2.

Strain plays an important role for the optical properties of monolayer transition metal dichalcogenides (TMDCs). Here, we investigate strain effects in a monolayer MoSe2 sample with a large bubble region using µ-Raman, second harmonic generation (SHG), µ-photoluminescence and magneto µ-photoluminescence at low temperature. Remarkably, our results reveal the presence of a non-uniform strain field and the observation of emission peaks at lower energies which are the signatures of exciton and trion quasiparticles red-shifted by strain effects in the bubble region, in agreement with our theoretical predictions. Furthermore, we have observed that the emission in the strained region decreases the trion binding energy and enhances the valley g-factors as compared to non-strained regions. Considering uniform biaxial strain effects within the unit cell of the TMDC monolayer (ML), our first principles calculations predict the observed enhancement of the exciton valley Zeeman effect. In addition, our results suggest that the exciton-trion fine structure plays an important role for the optical properties of strained TMDC ML. In summary, our study provides fundamental insights on the behaviour of excitons and trions in strained monolayer MoSe2 which are particularly relevant to properly characterize and understand the fine structure of excitonic complexes in strained TMDC systems/devices.

Cross-section profile of the nonlinear refractive index of Gorilla Glass obtained by nonlinear ellipse rotation measurements.

In this work we determined the influence of potassium-to-sodium ion exchange in the nonlinear refractive value (n2) of Corning's Gorilla Glass (GG). Due to the production process, GG has a rich potassium surface in comparison to the original sodium matrix glass. In order to determine the nonlinear cross-section profile, we have used a highly sensitive nonlinear elliptical rotation spatial measurement. Using a simple model, where the nonlinearity varies exponentially with depth, we observed that the value of the nonlinear refraction at the surface is about 22% greater than that of the matrix interior with a penetration depth constant of ∼50 µm.

Third-harmonic generation at the interfaces of a cuvette filled with selected organic solvents.

We report on the third-harmonic generation (THG) of tightly focused femtosecond laser pulses at the interfaces of a cuvette filled with organic solvents. Such a system presents four interfaces separating two materials of different refractive indices and third-order nonlinear susceptibilities where the THG takes place because the symmetry around the focus is broken. We selected two cuvettes (silica and B270 crown glass) filled with different organic solvents (acetone, chloroform, and dimethyl sulfoxide) in order to have a variety of interfaces with different linear and nonlinear optical properties. For some of the peaks, the self-focusing modifies the expected cubic power law dependence for THG and as a consequence the four peak profiles may be quite uneven. Although the THG is due to the electronic part of the nonlinear susceptibility, it can suffer from the influence of the self-focusing effect, a Kerr nonlinearity that can have both instantaneous electronic and slow nuclear contributions. This mixture of two distinct third-order nonlinear processes was never considered for such interfaces. All the THG signals could be understood by taking into account the self-focusing effect. Furthermore, the nonlinear refractive indices, n(2), and third-order nonlinear susceptibilities of the solvents, χ((3)), could be determined simultaneously by the THG signals using the cuvette walls as a reference.

Accurate measurement of nonlinear ellipse rotation using a phase-sensitive method.

We report on the accurate measurement of nonlinear ellipse rotation (NER) by means of a phase-sensitive method employing a dual-phase lock-in. The magnitudes and signs of pure refractive electronic nonlinearities of silica and BK7 were determined with this new method using 150 femtosecond (fs) laser pulses at 775 nm. Experimental and theoretical analyses of the NER signal were carried out and the results were compared to those obtained with the Z-scan technique.

Influence of self-focusing of ultrashort laser pulses on optical third-harmonic generation at interfaces.

We report on the third-harmonic generation of femtosecond laser pulses at interfaces. We measured slabs of different types of optical glasses and demonstrated that the asymmetric intensity profile observed for a tightly focused beam can be explained by self-focusing effects.

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.

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.

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.

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.

Precise control of superluminal and slow light propagation by transverse phase modulation.

We have used a heterodyne Z-scan technique to produce both superluminal and slow light propagation in media that present either thermal or Kerr nonlinearities. The sample position determines the magnitude and sign of the group velocity and this property was used to control it, with an experimental setup much simpler than those previously reported in similar investigations. The observed effect is attributed to the transverse phase modulation produced by a focused Gaussian beam, and is capable of producing both positive and negative group velocities in the range 1.5 m/s < |upsilon(g)| < c.

Nonlinear absorption dynamics in tetrapyridyl metalloporphyrins.

Nonlinear absorption dynamics of Zn(2+), Cu(2+), and Ni(2+) tetrapyridyl porphyrins in chloroform/methanol solutions were investigated at 532 nm with the Z-scan technique. Additional techniques such as UV-vis absorption spectroscopy and time-resolved fluorescence were used to obtain parameters that are important for the analysis of the population dynamics. A marked difference was observed in the nonlinear absorption and excited-state dynamics of closed (ZnTPyP)- and open-shell metalloporphyrins (CuTPyP and NiTPyP). ZnTPyP presents a reverse saturable absorption whose dynamics can be completely described by means of a simple five-energy-level diagram. On the other hand, CuTPyP and NiTPyP have a different excited-state dynamics, presenting a saturable absorption behavior and faster relaxation rates that were attributed to the presence of unfilled d shells of the central ion.

In situ UV-vis absorbance measurements for Langmuir films of poly[4'-[[2-(methacryloyloxy)-ethyl]ethylamino]-2-chloro-4-nitroazobenzene] (HPDR13) azopolymer.

In situ UV-vis absorbance measurements are used to investigate aggregation in Langmuir films from the azopolymer poly[4'-[[2-(methacryloyloxy)-ethyl]ethylamino]-2-chloro-4-nitroazobenzene] (HPDR13), a methacrylate derivative of DR13. The level of aggregation in a Langmuir film is intermediate between that of HPDR13 in chloroform solution and in a deposited LB film, as expected. Absorption is negligible at large areas per monomer, and starts to increase at a critical area that is the same as the one obtained in surface potential isotherms, being close to twice the area per monomer for a condensed film. This indicates that the onset for light absorption coincides with a critical packing density where monolayer structuring occurs and there is a sharp change in the effective dielectric constant of the film/water interface. Consistent with a featureless pressure-area isotherm for HPDR13, denoting no significant molecular rearrangement upon film compression, the UV-vis spectra did not vary with the surface pressure. The intensity of absorbed light increased, though, as the film was compressed owing to a higher density of chromophores. At higher subphase temperatures, larger flexibility of HPDR13 chains led to a more compact arrangement, causing the area per monomer to decrease and the absorbed light to increase-with approximately opposite trends.

Light-induced storage in layer-by-layer films of chitosan and an azo dye.

The buildup of layer-by-layer (LBL) films from chitosan and the azodye Ponceau-S (PS) was investigated under various experimental conditions, and the resulting films were used in optical storage experiments. The kinetics for the writing process in optical storage was faster for LBL films prepared at low pHs, probably because the films had a larger free volume for isomerization of the chromophores. The nanostructured nature of the LBL films also affected the crystallinity of chitosan, which was considerably decreased in this type of film as chitosan became protonated because of the electrostatic interactions between adjacent layers.

High-efficiency multipass optical limiter.

We report experimental results on a highly efficient optical limiter that uses a three-mirror, multipass ring configuration. The optical limiter's enhanced performance is based on the accumulative effect that is achieved when the laser beam passes through the sample several consecutive times. Its feasibility was demonstrated for media with different limiting action processes, namely, reverse saturable absorption, nonlinear scattering, and thermal lensing. We employed a frequency-doubled, Q-switched, 10-ns Nd:YAG laser operating at a 5-Hz repetition rate.

Generation of broadband VUV light using third-order cascaded processes.

We report the first demonstration of broadband VUV light generation through cascaded nonlinear wave mixing in a gas. Using a hollow-fiber geometry to achieve broad-bandwidth phase-matching, frequency conversion of ultrashort-pulse Ti:sapphire laser pulses from the visible into the deep UV around 200 and 160 nm is achieved. A new type of quasi-phase-matching is also observed in the VUV for the first time. Conversion using cascaded processes exhibits higher efficiencies, shorter pulse durations, and broader bandwidths than other schemes for generating light in the deep UV, and will enable many applications in science and technology.

Shaped-pulse optimization of coherent emission of high-harmonic soft X-rays

When an intense laser pulse is focused into a gas, the light-atom interaction that occurs as atoms are ionized results in an extremely nonlinear optical process--the generation of high harmonics of the driving laser frequency. Harmonics that extend up to orders of about 300 have been reported, some corresponding to photon energies in excess of 500 eV. Because this technique is simple to implement and generates coherent, laser-like, soft X-ray beams, it is currently being developed for applications in science and technology; these include probing the dynamics in chemical and materials systems and imaging. Here we report that by carefully tailoring the shapes of intense light pulses, we can control the interaction of light with an atom during ionization, improving the efficiency of X-ray generation by an order of magnitude. We demonstrate that it is possible to tune the spectral characteristics of the emitted radiation, and to steer the interaction between different orders of nonlinear processes.

A comparative study of nanosecond and picosecond laser ablation in enamel: morphological aspects.

OBJECTIVE: We have investigated and compared the main morphological features of human enamel tissue under Nd:YAG nanosecond and picosecond laser ablation. BACKGROUND DATA: The use of ultrashort laser pulses on teeth ablation is an alternative to avoid overheating and presents the advantage of minimizing the volume of damaged material during laser ablation. Comparison of the morphology obtained in laser ablation using nanosecond and picosecond laser pulses is a way to investigate the advantages of ultrashort laser pulses for ablation. METHODS: Trains of pulses with picosecond duration from a Q-switched and mode-locked Nd:YAG laser and pulses with nanosecond duration from a Q-switched Nd:YAG laser, both operating at 15 Hz kept at the same average power, were focused in human sound molars for 30 sec. Drilled holes with different morphological characteristics were observed using several laser intensity regimes. Enamel surfaces were examined using a scanning electron microscope (SEM) and their morphological characteristics compared. RESULTS: An interesting contrast between the morphology of the enamel when treated with different level of laser power and pulse duration was observed. Picosecond pulses promote a better-defined material removal with a minimum intermediate region, whereas nanosecond pulses at the equivalent average power level cause a large intermediate modified region between ablated and normal tissue, as well as a complete superficial modification of the existent original structure. CONCLUSION: Our results show an important correlation between the surface morphology and the pulse width of the lasers, suggesting advantages toward the use of ultrashort laser pulses in dentistry.

Characterization of enamel and dentin response to Nd:YAG picosecond laser ablation.

OBJECTIVE: We investigated the main characteristics of human dental tissue under Nd:YAG picosecond laser ablation. SUMMARY BACKGROUND DATA: The use of ultrashort laser pulses for teeth ablation prevents overheating and is an alternative for mechanical material removal; it also minimizes the volume of damaged material. METHODS: Laser pulses of picosecond at 15 Hz repetition rates from a Q-switched and mode-locked Nd:YAG laser were focused on sound human molars for 30 seconds. Variation of light intensity in the pulse train allowed us to obtain drilled holes with different characteristics. Enamel and dentin surfaces were examined by optical and scanning electron microscope (SEM). The samples consisted of three sound human molars. The ablation rate was determined after taking an average of all samples. RESULTS: Images from the SEM showed an interesting contrast between the morphology of the ablated enamel and dentin regions. In enamel, the ablated region appears to be more superficial than in dentin. The dentin fragility normally causes cracks that originate in the ablated region. The ablation rates in both enamel and dentin demonstrate a saturation behavior as the laser intensity increases. Furthermore, the ablation rate in dentin is about eight times greater than in enamel for the same laser fluence. CONCLUSION: Our results show an important correlation between the surface morphology and the pulsed laser fluence, which is compatible to the ablation mechanisms presented when ultrashort laser pulses are used.