Femtosecond Two-photon Research Articles

Femtosecond Two-Photon Photopolymerization—Creating 3D Microstructures for Optical Applications

Femtosecond Two-Photon Photopolymerization—Creating 3D Microstructures for Optical Applications

Abruptly Autofocusing Vortex Beams for Rapid Controllable Femtosecond Two-Photon Polymerization.

Micro-fabrication based on structured-beam-assisted Two-Photon Polymerization (2 PP) provides a rapid and flexible method for the manufacture of microstructures with complex morphologies. The tunable Abruptly Autofocusing Vortex (AAFV) beams were designed theoretically and generated experimentally based on a single-phase-only Spatial Light Modulator (SLM). Their specific spatial intensity distributions were further utilized to assist the fabrication of a bowl-shaped Three-Dimensional (3D) micro-trap array via 2 PP with a one-step exposure technique. Finally, the fabricated microstructures act as a novel tool for the trapping and spatial positioning of micro-particles with different diameters, which shows potential applications in fiber optics and cell study.

Temperature Measurements in Heated Gases and Flames Using Carbon Monoxide Femtosecond Two-Photon Laser-Induced Fluorescence

Temperature Measurements in Heated Gases and Flames Using Carbon Monoxide Femtosecond Two-Photon Laser-Induced Fluorescence

Ammonia Measurements with Femtosecond Two-Photon Laser-Induced Fluorescence in Premixed NH3/Air Flames

Ammonia (NH3), which can be a hydrogen carrier, is a promising alternative to fossil fuels in the future carbon-free economy. In situ techniques feasible for the remote and non-intrusive detection of NH3 will provide strong support for developing clean NH3 combustion. Here, we demonstrated a femtosecond two-photon laser-induced fluorescence (fs-TPLIF) technique for interference-free in situ NH3 measurements in laminar premixed NH3/air flames. The two-head band of NH3 at ∼565 nm was observed, which verifies the feasibility of fs-TPLIF for NH3 measurements in a combustion environment. The single-shot NH3 fs-TPLIF images with efficient signal-to-noise ratios were obtained. The variation of the thickness of the reaction zone with the equivalence ratio of NH3 flames was also obtained. As a result of the broad line width of the femtosecond laser, the OH fluorescence was also observed together with the NH3 fluorescence. The potential of fs-TPLIF for simultaneous measurements of NH3 and OH with only one laser was analyzed. The laser power dependence of NH3 and NH emissions was investigated. The radial distributions of NH3, NH, and OH in the flame were also discussed. This work is the first attempt of fs-TPLIF for NH3 measurements in a combustion environment, and the results indicate that fs-TPLIF is a feasible tool for NH3 measurements in combustion diagnostics. (Less)

Cycloreversion Reaction of a Fulgide Derivative in Higher Excited States Attained by Femtosecond Two-Photon Pulsed Excitation

The mechanism of the cycloreversion reaction of a fulgide derivative in the higher excited states (Sn states) pumped by the stepwise two-photon excitation was investigated by femtosecond transient absorption spectroscopy. The first photon excitation of the ground state by the visible light led to the production of the Franck–Condon 1B state, which underwent internal conversion to the 2A state with 100 fs time constant and the structural reorganization accompanied with the vibrational cooling with 1.5 ps time constant. After these relaxation processes, the 2A state underwent the cycloreversion reaction (11% reaction yield) with competitive nonradiative as well as radiative deactivation processes into the ground state with a time constant of 10 ps. Under the double-pulse pump condition, whereas the excitation of the 1B state induced no remarkable cycloreversion reaction, the excitation of the 2A state resulted in the marked enhancement of the cycloreversion reaction with a reaction quantum yield of ca. 80% ...

Femtosecond, two-photon, laser-induced fluorescence (TP-LIF) measurement of CO in high-pressure flames.

Quantitative, kiloherz-rate measurement of carbon monoxide mole fractions by femtosecond two-photon, laser-induced fluorescence (TP-LIF) was demonstrated in high-pressure, luminous flames over a range of fuel-air ratios. Femtosecond excitation at 230.1nm was used to pump CO two-photon rovibrational X1Σ+→B1Σ+ transitions in the Hopfield-Birge system and avoid photolytic interferences with excitation irradiance ∼1.7×1010 W/cm2. The effects of excitation wavelength, detection scheme, and potential sources of de-excitation were also assessed to optimize the signal-to-background and signal-to-noise ratios and achieve excellent agreement with theoretically predicted CO mole fractions at low and high pressure.

PH Effect on Two-Photon Cross Section of Highly Fluorescent Dyes Using Femtosecond Two-Photon Induced Fluorescence.

Effect of solution pH on two-photon absorption cross-section of highly fluorescent Coumarin and Rhodamine dyes with high repetition rate femtosecond laser pulses at 780nm is presented using two-photon induced fluorescence technique. A correspondence in the measured two-photon and single-photon cross-section values is seen when the pH changes from acidic to basic conditions (pH=2-10) for solutions in 1:1 water-ethanol binary mixture. By plotting changes in the single-photon and two-photon fluorescence in this pH range, the excited state pKa values are found. The ground state pKa values are also affected by the protonation deprotonation equilibrium as a result of variation in pH from acidic to basic, which are characterized by changes in absorbance spectra. Most of these single-photon and two-photon induced fluorescence spectra show characteristic blue shifts. Different fluorescence quantum yields calculated at each pH reflect a change in structure corresponding to their associated properties as a result of acid base equilibrium.

Symmetry Breaking in Platinum Acetylide Chromophores Studied by Femtosecond Two-Photon Absorption Spectroscopy.

We study instantaneous two-photon absorption (2PA) in a series of nominally quasi-centrosymmetric trans-bis(tributylphosphine)-bis-(4-((9,9-diethyl-7-ethynyl-9H-fluoren-2-yl) ethynyl)-R)-platinum complexes, where 11 different substituents, R = N(phenyl)2(NPh2), NH2, OCH3, t-butyl, CH3, H, F, CF3, CN, benzothiazole, and NO2, represent a range of electron-donating (ED) and electron-withdrawing (EW) strengths, while the Pt core acts as a weak ED group. We measure the 2PA cross section in the 540-810 nm excitation wavelength range by complementary femtosecond two-photon excited fluorescence (2PEF) and nonlinear transmission (NLT) methods and compare the obtained values to those of the Pt-core chromophore and the corresponding noncentrosymmetric side group (ligand) chromophores. Peak 2PA cross sections of neutral and ED-substituted Pt complexes occur at S0 → Sn transitions to higher energy states, above the lowest-energy S0 → S1 transition, and the corresponding values increase systematically with increasing ED strength, reaching maximum value, σ2 ∼ 300 GM (1 GM = 10-50 cm4 s), for R = NPh2. At transition energies overlapping with the lowest-energy S0 → S1 transition in the one-photon absorption (1PA) spectrum, the same neutral and ED-substituted Pt complexes show weak 2PA, σ2 < 30-100 GM, which is in agreement with the nearly quadrupolar structure of these systems. Surprisingly, EW-substituted Pt complexes display a very different behavior, where the peak 2PA of the S0 → S1 transition gradually increases with increasing EW strength, reaching values σ2 = 700 GM for R = NO2, while in the S0 → Sn transition region the peak 2PEF cross section decreases. We explained this effect by breaking of inversion symmetry due to conformational distortions associated with low energy barrier for ground-state rotation of the ligands. Our findings are corroborated by theoretical calculations that show large increase of the permanent electric dipole moment change in the S0 → S1 transition when ligands with strong EW substituents are twisted by 90° relative to the planar chromophore. Our NLT results in the S0 → S1 transition region are quantitatively similar to those obtained from the 2PEF measurement. However, at higher transition energy corresponding to S0 → Sn transition region, the NLT method yields effective multiphoton absorption stronger than the 2PEF measurement in the same systems. Such enhancement is observed in all Pt complexes as well as in all ligand chromophores studied, and we tentatively attribute this effect to nearly saturated excited-state absorption (ESA), which may occur if 2PA from the ground state is immediately followed by strongly allowed 1PA to higher excited states.

Femtosecond Two-Photon Detachment of Cu− Studied By Photoelectron Imaging

The wavelength dependence of photoelectron angular distributions (PADs) of two-photon detachment of Cu− has been directly studied by using the photoelectron map imaging. Results show that for the laser field intensity of 6.0×1010 W/cm2, PADs exhibit dramatic change with the external field wavelength. Comparison between the experimental observation and the lowest-order perturbation theory prediction indicates that the pattern of PADs can be explained by the interference of the s and d partial waves in the final state. Relative contributions of s and d partial waves in the two-photon detachment at different laser wavelengths are obtained.

Femtosecond Two-Photon Ionization and Solvated Electron Geminate Recombination in Liquid-to-Supercritical Ammonia

The first-ever femtosecond pump-probe study is reported on solvated electrons that were generated by multiphoton ionization of neat fluid ammonia. The initial ultrafast ionization was carried out with 266 nm laser pulses and was found to require two photons. The solvated electron was detected with a femtosecond probe pulse that was resonant with its characteristic near-infrared absorption band around 1.7 μm. Furthermore, the geminate recombination dynamics of the solvated electron were studied over wide ranges of temperature (227 K ≤ T ≤ 489 K) and density (0.17 g cm(-3) ≤ ρ ≤ 0.71 g cm(-3)), thereby covering the liquid and the supercritical phase of the solvent. The electron recombines in a first step with ammonium cations originating from the initial two-photon ionization thereby forming transient ion-pairs (e(am)(-)·NH(4)(+)), which subsequently react in a second step with amidogen radicals to reform neutral ammonia. The escape probability, i.e., the fraction of solvated electrons that can avoid the geminate annihilation, was found to be in quantitative agreement with the classical Onsager theory for the initial recombination of ions. When taking the sequential nature of the ion-pair-mediated recombination mechanism explicitly into account, the Onsager model provides a mean thermalization distance of 6.6 nm for the solvated electron, which strongly suggests that the ionization mechanism involves the conduction band of the fluid.

Large Femtosecond Two-Photon Absorption Cross Sections of Fullerosome Vesicle Nanostructures Derived from a Highly Photoresponsive Amphiphilic C60-Light-Harvesting Fluorene Dyad

We demonstrated ultrafast femtosecond nonlinear optical (NLO) absorption characteristics of bilayered fullerosome vesicle nanostructures derived from molecular self-assembly of amphiphilic oligo(ethylene glycolated) C(60)-(light-harvesting diphenylaminofluorene antenna). Fullerene conjugates were designed to enhance photoresponse in a femtosecond time scale by applying an isomerizable periconjugation linker between the C(60) cage and diphenylaminofluorene antenna subunit in an intramolecular contact distance of only < 3.0 Å. Morphology of C(60)(>DPAF-EG(12)C(1))-based fullerosome nanovesicles in H(2)O was characterized to consist of a bilayered shell with a sphere diameter of 20-70 nm and a chromophore shell-width of 9.0-10 nm, fitting well with a head-to-head packing configuration of the molecular length. At the estimated effective nanovesicle concentration as low as 5.5 × 10(-8) MV (molecular molar concentration of 5.0 × 10(-4) M) in H(2)O, two-photon absorption (2PA) phenomena were found to be the dominating photophysical events showing a large molar concentration-insensitive 2PA cross-section value equivalent to 8500 GM in a form of nanovesicles, on average. The observed NLO characteristics led to a sharp trend of efficient light-transmittance intensity reduction at the input laser intensity above 100 GW/cm(2).

Ca 2+ Fluorescence Imaging with Pico- and Femtosecond Two-Photon Excitation: Signal and Photodamage

The signal and limitations of calcium florescence imaging using nonresonant multiphoton absorption of near-infrared femto- and picosecond laser pulses were examined. The fluorescence changes of various Ca 2+-indicators induced by transient increases of the intradendritic calcium concentration were evaluated by evoking physiological activity in neocortical neurons in rat brain slices. Photodamage was noticeable as irreversible changes in the parameters describing the calcium fluorescence transients. At higher two-photon excitation rates, a great variety of irregular functional and structural alterations occurred. Thus, signal and observation time were limited by phototoxic effects. At lower excitation rates, photodamage accumulated linearly with exposure time. Femtosecond and picosecond laser pulses were directly compared with respect to this cumulative photodamage. The variation of the pulse length at a constant two-photon excitation rate indicated that a two-photon excitation mechanism is mainly responsible for the cumulative photodamage within the investigated window of 75 fs to 3.2 ps. As a direct consequence, at low excitation rates, the same image quality is achieved irrespective of whether two-photon Ca 2+-imaging is carried out with femto- or picosecond laser pulses.

Femtosecond Two-photon Excited Fluorescence of Melanin

Femtosecond Two-photon Excited Fluorescence of Melanin