New Two-Photon Absorbing Squaraine Derivative with Efficient Near-Infrared Fluorescence, Superluminescence, and High Photostability.

The nature of linear photophysical and nonlinear optical properties of a new squaraine derivative 2,4-bis[4-(azetidyl)-2-hydroxyphenyl]squaraine (1) with efficient near-infrared (NIR) emission was comprehensively analyzed based on spectroscopic, photochemical, and two-photon absorption (2PA) measurements, along with quantum chemical analysis. The steady-state absorption, fluorescence, and excitation anisotropy spectra of 1 and its fluorescence emission lifetimes revealed the multiple aspects of the electronic structure of 1, including the relative orientations of the main transition dipoles, effective rotational volumes in solvents of different polarities, and a maximum molar extinction of 1.35 × 10-5 M-1·cm-1, which is unusually small for similar symmetric squaraines. The degenerate 2PA spectrum of 1 was obtained over a broad spectral range under femtosecond excitation, using standard open-aperture Z-scan and two-photon induced fluorescence methods, revealing maximum 2PA cross sections of ∼400 GM. Squaraine 1 exhibited efficient superluminescence emission in the polar solvent (dichloromethane) at room temperature under femtosecond pumping conditions. Quantum chemical analysis of the electronic structure of 1 was performed using the DFT/TD-DFT level of theory and found to be in good agreement with experimental data. The new squaraine derivative 1 displayed high fluorescence quantum yield, efficient NIR superluminescence, large 2PA cross sections, and high photostability with a photodecomposition quantum yield ∼4 × 10-6, suggesting its potential for applications in two-photon fluorescent bioimaging and lasing.

Refraction of space-time wave packets in a dispersive medium.

Space-time (ST) wave packets are a class of pulsed optical beams whose spatiotemporal spectral structure results in propagation invariance, tunable group velocity, and anomalous refractive phenomena. Here, we investigate the refraction of ST wave packets normally incident onto a planar interface between two dispersive, homogeneous, isotropic media. We formulate a new, to the best of our knowledge, refractive invariant for ST wave packets in this configuration, from which we obtain a law of refraction that determines the change in their group velocity across the interface. We verify this new refraction law in ZnSe and CdSe, both of which manifest large chromatic dispersion at near-infrared frequencies in the vicinity of their band edges. ST wave packets can thus be utilized in nonlinear optics for bridging large group-velocity mismatches in highly dispersive scenarios.

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.

Transient mid-IR nonlinear refraction in air.

We use the polarization-sensitive, time-resolved Beam-Deflection technique to measure the nonlinear refraction of air, exciting in both the near and mid-IR and probing in the mid-IR. This gives us the first measurements for air using both excitation and probe in the mid-IR, and we find no dispersion of the bound-electronic nonlinear refractive index, n2,el(λp;λe), assuming, as has been shown earlier, that the nuclear rotational nonlinear refraction is nearly dispersionless. From these data, we can model the pulsewidth dependence of the effective nonlinear refractive index, n2,eff, i.e., as would be measured by a single beam. Interestingly, n2,eff is maximized for a pulsewidth of approximately 0.5 ps. The position of this maximum is nearly independent of pressure while its magnitude decreases with increasing pressure and temperature. From the measurements and modeling, we predict the nonlinear refraction in the atmosphere at different altitudes.

Highly Conjugated, Fused-Ring, Quadrupolar Organic Chromophores with Large Two-Photon Absorption Cross-Sections in the Near-Infrared.

The two-photon absorption (2PA) properties are investigated for two series of organic, π-conjugated, fused-ring, quadrupolar A-π-D-π-A chromophores of the type originally developed as nonfullerene acceptors for organic photovoltaics. These molecules are found to exhibit large nondegenerate two-photon absorption (ND2PA) cross-sections (ca. 6-27 × 103 GM) in the near-infrared (NIR). In the first series, involving molecules of varying core size, ND2PA spectra and cross-sections characterized by femtosecond ND2PA spectroscopy in chloroform solutions reveal that increases in core size, and thus conjugation length, leads to substantially red-shifted and enhanced 2PA. In a second series, variation of the strength of the terminal acceptor (A) with constant core size (seven rings, indacene-based) led to less dramatic variation in the 2PA properties. Among the two core types studied, compounds in which the donor has a thieno[3,2-b]thiophene center demonstrate larger 2PA cross-sections than their indacene-centered counterparts, due to the greater electron-richness of their cores amplifying intramolecular charge transfer. Excited-state absorption (ESA) contributions to nonlinear absorption measured by open-aperture Z-scans are deduced for some of the compounds by analyzing the spectral overlap between 2PA bands and NIR ESA transitions obtained by ND2PA and transient absorption measurements, respectively. ESA cross-sections extracted from transient absorption and irradiance-dependent open-aperture Z-scans are in reasonable agreement, and their moderate magnitudes (ca. 10-21 m2) suggest that, although ESA contributions are non-negligible, the effective response is predominantly instantaneous 2PA.

Nonlinear Optics: feature issue introduction.

This joint issue of Optics Express and Optical Materials Express features 18 state-of-the art articles that witness actual developments in nonlinear optics, including those by authors who participated in the international conference Nonlinear Optics held in Waikoloa, Hawaii from July 15 to 19, 2019. As an introduction, the editors provide a summary of these articles that cover all aspects of nonlinear optics, from basic nonlinear effects and novel frequency windows to innovative nonlinear materials and devices, thereby paving the way for new nonlinear optical concepts and forthcoming applications.

Three-photon absorption spectra of zinc blende semiconductors: theory and experiment: erratum.

We provide a correction to the spectral dependence of the three-photon absorption in zinc-blende semiconductors using Kane's 4-band model in Opt. Lett.33, 2626 (2008).OPLEDP0146-959210.1364/OL.33.002626.

Cationic Polyelectrolyte for Anionic Cyanines: An Efficient Way To Translate Molecular Properties into Material Properties.

In this work, a new phosphonium-containing cationic polyelectrolyte (PE1) has been rationally designed and developed via a facile click-chemistry type postfunctionalization, which can form complexes with highly polarizable anionic cyanines to significantly reduce the strong and random cyanine-cyanine interactions (i.e., aggregation) in the solid-state. This material design strategy enables an efficient translation of the favorable molecular properties of cyanines into macroscopic material properties. One of such complexes exhibits a very large third-order susceptibility over 10-10 esu with low nonlinear optical loss suitable for all optical signal processing.

Electronic Nature of Neutral and Charged Two-Photon Absorbing Squaraines for Fluorescence Bioimaging Application.

The electronic properties of neutral 2,4-bis(4-bis(2-hydroxyethyl) amino-2-hydroxy-6-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)squaraine (1) and charged 2-((3-octadecylbenzothiazol-2(3H)-ylidene)methyl)-3-oxo-4-((3-(4-(pyridinium-1-yl)butyl)benzo-thiazol-3-ium-2-yl)methylene)cyclobut-1-enolate iodide (2) squaraine derivatives were analyzed based on comprehensive linear photophysical, photochemical, nonlinear optical studies (including two-photon absorption (2PA) and femtosecond transient absorption spectroscopy measurements), and quantum chemical calculations. The steady-state absorption, fluorescence, and excitation anisotropy spectra of these new squaraines revealed the values and mutual orientations of the main transition dipoles of 1 and 2 in solvents of different polarity, while their role in specific nonlinear optical properties was shown. The degenerate 2PA spectra of 1 and 2 exhibited similar shapes, with maximum cross sections of ∼300-400 GM, which were determined by the open aperture Z-scan method over a broad spectral range. The nature of the time-resolved excited-state absorption spectra of 1 and 2 was analyzed using a femtosecond transient absorption pump-probe technique and the characteristic relaxation times of 4-5 ps were revealed. Quantum chemical analyses of the electronic properties of 1 and 2 were performed using the ZINDO/S//DFT theory level, affording good agreement with experimental data. To demonstrate the potential of squaraines 1 and 2 as fluorescent probes for bioimaging, laser scanning fluorescence microscopy images of HeLa cells incubated with new squaraines were obtained.

Nonlinear refraction and absorption measurements of thin films by the dual-arm Z-scan method.

We extend the recently developed dual-arm Z-scan to increase the signal-to-noise ratio (SNR) for measuring the nonlinear refraction (NLR) of thin films on thick substrates. Similar to the case of solutes in solution, the phase shift due to NLR in a thin film can often be dominated by the phase shift due to NLR in the much thicker substrate. SNR enhancement is accomplished by simultaneously scanning a bare substrate and the film plus substrate in two separate but identical Z-scan arms. The subtraction of these signals taken simultaneously effectively cancels the nonlinear signal from the substrate, leaving only the signal from the film. More importantly, the SNR is increased since the correlated noise from effects such as beam-pointing instabilities cancels. To show the versatility of the dual-arm Z-scan method, we perform measurements on semiconductor and organic thin films, some less than 100 nm thick and with thicknesses up to 4 orders of magnitude less than the substrate.

Introduction: Nonlinear Optics (NLO) 2017 feature issue.

The editors introduce the feature issue on "Nonlinear Optics 2017," based on the topics presented at the NLO 2017 conference, which was held in Waikoloa, Hawaii, USA from July 17-21, 2017. This feature issue is jointly published by Optics Express and Optical Materials Express.

Engineered nonlinear materials using gold nanoantenna array.

Gold dipole nanoantennas embedded in an organic molecular film provide strong local electromagnetic fields to enhance both the nonlinear refractive index (n2) and two-photon absorption (2PA) of the molecules. An enhancement of 53× for 2PA and 140× for nonlinear refraction is observed for BDPAS (4,4'-bis(diphenylamino)stilbene) at 600 nm with only 3.7% of gold volume fraction. The complex value of the third-order susceptibility enhancement results in a sign change of n2 for the effective composite material relative to the pure BDPAS film. This complex nature of the enhancement and the tunability of the nanoantenna resonance allow for engineering the effective nonlinear response of the composite film.

Dispersion of nondegenerate nonlinear refraction in semiconductors.

We use our recently developed beam-deflection technique to measure the dispersion of the nondegenerate nonlinear refraction (NLR) of direct-gap semiconductors. The magnitude and sign of the NLR coefficient n2(ωa; ωb) are determined over a broad spectral range for different values of nondegeneracy. In the extremely nondegenerate case, n2(ωa; ωb) is positively enhanced near the two-photon absorption (2PA) edge and is significantly larger than its degenerate counterpart, suggesting applications for nondegenerate all-optical switching. At higher photon energies within the 2PA regime, n2(ωa; ωb) switches sign to negative over a narrow wavelength range. This strong anomalous nonlinear dispersion provides large phase modulation of a femtosecond pulse with bandwidth centered near the zero-crossing frequency. The measured nondegenerate dispersion closely follows our earlier predictions based on nonlinear Kramers-Kronig relations [Sheik-Bahae et. al, IEEE J. Quant. Electron. 30, 249 (1994)].

Observation of Nondegenerate Two-Photon Gain in GaAs.

Two-photon lasers require materials with large two-photon gain (2PG) coefficients and low linear and nonlinear losses. Our previous demonstration of large enhancement of two-photon absorption in semiconductors for very different photon energies translates directly into enhancement of 2PG. We experimentally demonstrate nondegenerate 2PG in optically excited bulk GaAs via femtosecond pump-probe measurements. 2PG is isolated from other pump induced effects through the difference between measurements performed with parallel and perpendicular polarizations of pump and probe. An enhancement in the 2PG coefficient of nearly 2 orders of magnitude is reported. The results point a possible way toward two-photon semiconductor lasers.

Beam deflection measurement of bound-electronic and rotational nonlinear refraction in molecular gases: erratum.

We provide an updated comparison of second hyperpolazability of carbon disulfide reported in [Opt. Express23(17), 22224 (2015)10.1364/OE.23.022224Optica3(6), 657 (2016)10.1364/OPTICA.3.000657].

Facile Incorporation of Pd(PPh3)2Hal Substituents into Polymethines, Merocyanines, and Perylene Diimides as a Means of Suppressing Intermolecular Interactions.

Compounds with polarizable π systems that are susceptible to attack with nucleophiles at C-Hal (Hal = Cl, Br) bonds react with Pd(PPh3)4 to yield net oxidative addition. X-ray structures show that the resulting Pd(PPh3)2Hal groups greatly reduce intermolecular π-π interactions. The Pd-functionalized dyes generally exhibit solution-like absorption spectra in films, whereas their Hal analogues exhibit features attributable to aggregation.

Three-dimensional IR imaging with uncooled GaN photodiodes using nondegenerate two-photon absorption.

We utilize the recently demonstrated orders of magnitude enhancement of extremely nondegenerate two-photon absorption in direct-gap semiconductor photodiodes to perform scanned imaging of three-dimensional (3D) structures using IR femtosecond illumination pulses (1.6 µm and 4.93 µm) gated on the GaN detector by sub-gap, femtosecond pulses. While transverse resolution is limited by the usual imaging criteria, the longitudinal or depth resolution can be less than a wavelength, dependent on the pulsewidths in this nonlinear interaction within the detector element. The imaging system can accommodate a wide range of wavelengths in the mid-IR and near-IR without the need to modify the detection and imaging systems.

Beam deflection measurement of bound-electronic and rotational nonlinear refraction in molecular gases.

A polarization-resolved beam deflection technique is used to separate the bound-electronic and molecular rotational components of nonlinear refractive transients of molecular gases. Coherent rotational revivals from N(2), O(2), and two isotopologues of carbon disulfide (CS(2)), are identified in gaseous mixtures. Dephasing rates, rotational and centrifugal distortion constants of each species are measured. Polarization at the magic angle allows unambiguous measurement of the bound-electronic nonlinear refractive index of air and second hyperpolarizability of CS(2). Agreement between gas and liquid phase second hyperpolarizability measurements is found using the Lorentz-Lorenz local field correction.

Nonlinear Optical Properties of X(C6H5)4 (X = B(-), C, N(+), P(+)): A New Class of Molecules with a Negative Third-Order Polarizability.

Organic π-conjugated materials have been widely used for a variety of nonlinear optical (NLO) applications. Molecules with negative real components Re(γ) of the third-order polarizability, which leads to nonlinear refraction in macroscopic systems, have important benefits for several NLO applications. However, few organic systems studied to date have negative Re(γ) in the long wavelength limit, and all inorganic materials show positive nonlinear refraction in this limit. Here, we introduce a new class of molecules of the form X(C6H5)4, where X = B(-), C, N(+), and P(+), that have negative Re(γ). The molecular mechanism for the NLO properties in these systems is very different from those in typical linear conjugated systems: These systems have a band of excited states involving single-electron excitations within the π-system, several of which have significant coupling to the ground state. Thus, Re(γ) cannot be understood in terms of a simplified essential-state model and must be analyzed in the context of the full sum-over-states expression. Although Re(γ) is significantly smaller than that of other commonly studied NLO chromophores, the introduction of a new molecular architecture offering the potential for a negative Re(γ) introduces new avenues of molecular design for NLO applications.

Beam deflection measurement of time and polarization resolved ultrafast nonlinear refraction.

We modify the well-known photothermal beam deflection technique to study ultrafast nonlinearities. Using phase-sensitive detection we directly measure the temporal and polarization dynamics of nonlinear refraction (NLR) with sensitivity to optically induced phase changes of approximately λ/20,000. We use the relative polarization dependence of excitation and probe to separate the isotropic and reorientational components of the NLR.