Nonlinear Optical Excitation Research Articles

Tailoring of the polarization-resolved second harmonic generation in two-dimensional semiconductors

Abstract Second harmonic generation is a non-linear optical phenomenon in which coherent radiation with frequency ω interacts with a non-centrosymmetric material and produces coherent radiation at frequency 2ω. Owing to the exciting physical phenomena that take place during the non-linear optical excitation at the nanoscale, there is currently extensive research in the non-linear optical responses of nanomaterials, particularly in low-dimensional materials. Here, we review recent advancements in the polarization-resolved second harmonic generation propertied from atomically thin two-dimensional (2D) crystals and present a unified theoretical framework to account for their nonlinear optical response. Two major classes of 2D materials are particularly investigated, namely metal chalcogenides and perovskites. The first attempts to tune and control the second harmonic generation properties of such materials via the application of specific nanophotonic schemes are additionally demonstrated and discussed. Besides presenting recent advances in the field, this work also delineates existing limitations and highlights emerging possibilities and future prospects in this field.

Enhancing photon recycling of perovskite nanosheet by two-photon excitation

Nanometer scale light penetration depths of halide perovskite (HP) set an intrinsic limit on the performance improvement of optoelectronic devices. Here, we show that two-photon excitation can overcome this limit by markedly increasing the light penetration depth and significantly enhance photon recycling. Through a comparison study between one-photon and two-photon excitations by femtosecond laser pulses in a CsPbBr3 nanosheet, our results demonstrate that two-photon excitation can increase photocarrier transport distance by about 900 nm, which is even comparable to the photocarrier diffusion length. Our work provides substantial insights into the photon recycling of HP induced by nonlinear optical excitations, which can benefit the performance optimization of advanced optoelectronic devices.

Mapping Light-Dressed Floquet Bands by Highly Nonlinear Optical Excitations and Valley Polarization.

Ultrafast nonlinear optical phenomena in solids have been attracting a great deal of interest as novel methodologies for the femtosecond spectroscopy of electron dynamics and control of the properties of materials. Here, we theoretically investigate strong-field nonlinear optical transitions in a prototypical two-dimensional material, hBN, and show that the k-resolved conduction band charge occupation patterns induced by an elliptically polarized laser can be understood in a multiphoton resonant picture, but, remarkably, only if using the Floquet light-dressed states instead of the undressed matter states. Our work demonstrates that Floquet dressing affects ultrafast charge dynamics and photoexcitation even from a single pump pulse and establishes a direct measurable signature for band dressing in nonlinear optical processes in solids, opening new paths for ultrafast spectroscopy and valley manipulation.

Biotransformation of 1-nitro-2-phenylethane [Formula: see text] 2-phenylethanol from fungi species of the Amazon biome: an experimental and theoretical analysis.

Natural products and their biotransformation procedures are a powerful source of new chromophores with potential applications in fields like biology, pharmacology and materials science. Thus, this work discusses about the extraction procedure of 1-nitro-2-phenylethane (1N2PE) from Aniba canelilla, its biotransformation setup into 2-phenylethanol (2PE) using four fungi, Lasiodiplodia caatinguensis (phytopathogenic fungus from Citrus sinensis), Colletotrichum sp. (phytopathogenic fungus from Euterpe oleracea), Aspergillus flavus and Rigidoporus lineatus isolated from copper mining waste located in the interior of the Brazilian Amazon. A detailed experimental and theoretical vibrational analysis (IR and Raman) have allowed us to perform some charge transfer effects on the title compounds (push-pull effect) by monitoring specific vibrational modes of their electrophilic and nucleophilic molecular sites. The solvent interactions promote molecular conformations that affect the vibrational spectra of the donor and acceptor groups, as can be seen comparatively in the gas and aqueous solution spectra, an effect possibly related to the bathochromic shift in the calculated optical spectrum of the compounds. The nonlinear optical behavior shows that while the solvent reduces the response of 1N2PE, the response of 2PE increases the optical parameters, which presents low refractive index (n) and first hyperpolarizability. ([Formula: see text]) is almost eight times that reported for urea (42.79 a.u.), a common nonlinear optical material. Furthermore, the bioconversion goes from an electrophilic to a nucleophilic compound, affecting its molecular reactivity. 1N2PE was obtained from Aniba canelilla, whose essential oil is constituted of [Formula: see text] of 2PE. The A. canelilla essential oil was extracted under hydrodistillation. The biotransformation reactions were performed in autoclaved liquid media (100mL) composed of malt extract (2%) in 250mL Erlenmeyer flask. Each culture was incubated in an orbital shaker (130 rpm) at [Formula: see text]C during 7 days and after that, 50mg of 1N2PE (80%) were diluted in 100 [Formula: see text]L of dimethylsulfoxide (DMSO) and added to the reactions flasks. Aliquots (2mL) were removed using ethyl acetate (2mL) and analyzed by GC-MS (fused silica capillary col1umn, Rtx -5MS 30m [Formula: see text] 0.25 mm [Formula: see text] 0.25 [Formula: see text]m) in order to determine the amount of 1N2PE biotransformation. FTIR 1N2PE and 2PE spectra were obtained by attenuated total reflectance (ATR), using a Agilent CARY 630 spectrometer, in the spectral region 4000-650cm[Formula: see text]. The quantum chemical calculations were carried out in the Gaussian 09 program while the DICE code was used to perform the classical Monte Carlo simulations and generate the liquid environment using the classical All-Atom Optimized parameters for Liquid Simulations (AA-OPLS). All nonlinear optical properties, reactive parameters, and electronic excitations were calculated using the Density Functional Theory framework coupled to the standard 6-311++G(d,p) basis set.

Fast and direct optical dispersion estimation for ultrafast laser pulse compression.

In ultrashort pulse laser applications, optical dispersion seriously affects the energy concentration in the laser pulse duration and lowers the peak power. Accordingly, this study proposes a rapid dispersion estimation mechanism to facilitate the compensation of optical dispersion using a closed-loop control system. In the proposed approach, the optical dispersion information of the laser pulse is estimated directly from a frequency-resolved optical gating trace without the need for an iterative pulse-retrieval algorithm. In particular, the group delay dispersion (GDD) is determined from frequency and delay marginals, which are related to the laser spectrum and intensity autocorrelation, respectively, using a simple lookup table approach. The accuracy of the estimated GDD results is confirmed via a comparison with the spectral phase distribution of the electric field reconstructed using the principal component generalized projections algorithm. It is shown that the computation time of the proposed direct estimation method is around 13 times faster than that of the traditional iterative algorithm. It thus provides a feasible approach for enabling the real-time compensation of ultrafast laser pulse compression. Moreover, in a multiphoton-excited fluorescence imaging application, the proposed pulse compression mechanism yields an effective improvement in the intensity and contrast of the reconstructed image due to the increased nonlinear optical excitation efficiency of the optimized laser pulses.

Methylhydrazinium]2PbBr4, a Ferroelectric Hybrid Organic–Inorganic Perovskite with Multiple Nonlinear Optical Outputs

An expansive library of structurally complex two-dimensional (2D) and three-dimensional (3D) lead halide perovskites has emerged over the past decade, finding applications in various aspects of photon management: photovoltaics, photodetection, light emission, and nonlinear optics. Needless to say, the highest degree of structural plasticity enjoys the former group, offering a rich playground for modifications of relevant optoelectronic parameters such as exciton energy. Structural tailorability is reflected in the ease of modification of the chemistry of the organic layers residing between inorganic slabs. In this vein, we show that the introduction of methylhydrazinium cation (MHy+, CH3NH2NH2+) into 2D perovskite gives a material with a record low separation of the inorganic layers (8.91 Å at 300 K). Optical studies showed that MHy2PbBr4 features the most red-shifted excitonic absorption among all known A2PbBr4 compounds as well as a small exciton binding energy of 99.9 meV. MHy2PbBr4 crystallizes in polar Pmn21 symmetry at room emperature (phase III) and at 351 K undergoes a phase transition to modulated Pmnm phase (II) followed by another phase transition at 371 K to Pmnm phase (I). The ferroelectric property of room-temperature phase III is inferred from switching of the pyrocurrent, dielectric measurements, and optical birefringence results. MHy2PbBr4 exhibits multiple nonlinear optical phenomena such as second-harmonic generation, third-harmonic generation, two-photon excited luminescence, and multiphoton excited luminescence. Analysis of MHy2PbBr4 single-crystal luminescence spectra obtained through linear and nonlinear optical excitation pathways indicates that free exciton emission is readily probed by the ultraviolet excitation, whereas crumpled exciton emission is detected under two- and multiphoton excitation conditions. Overall, our results demonstrate that incorporation of MHy+ into the organic layer is an emergent strategy for obtaining a 2D perovskite with polar character and multifunctional properties.

Highly Asymmetric Optical Properties of β-Ga2O3 as Probed by Linear and Nonlinear Optical Excitation Spectroscopy

Highly asymmetric optical properties of b-Ga2O3 are investigated by polarization-dependent photoluminescence (PL) excitation spectroscopy for assessing its potential use for a novel ultraviolet emitter and nonlinear optical material. Based on power-dependent excitation and two-photon depth scan, it is demonstrated that the underlying mechanism for the PL occurring far below the bandgap is not caused by intrinsic polaron effects, but by excitonic recombination at extrinsic defect sites.

Dynamics of carbon nanotube-based mode-locking fiber lasers

Abstract Carbon nanotube (CNT) can work as excellent saturable absorber (SA) due to its advantages of fast recovery, low saturation intensity, polarization insensitivity, deep modulation depth, broad operation bandwidth, outstanding environmental stability, and affordable fabrication. Its successful application as SA has promoted the development of scientific research and practical application of mode-locked fiber lasers. Besides, mode-locked fiber laser constitutes an ideal platform for investigating soliton dynamics which exhibit profound nonlinear optical dynamics and excitation ubiquitous in many fields. Up to now, a variety of soliton dynamics have been observed. Among these researches, CNT-SA is a key component that suppresses the environmental perturbation and optimizes the laser system to reveal the true highly stochastic and non-repetitive unstable phenomena of the initial self-starting lasing process. This review is intended to provide an up-to-date introduction to the development of CNT-SA based ultrafast fiber lasers, with emphasis on recent progress in real-time buildup dynamics of solitons in CNT-SA mode-locked fiber lasers. It is anticipated that study of dynamics of solitons can not only further reveal the physical nature of solitons, but also optimize the performance of ultrafast fiber lasers and eventually expand their applications in different fields.

Fourier-domain mode-locked laser combined with a master-oscillator power amplifier architecture

Originally introduced in 2005 for high-speed optical coherence tomography, the rapidly wavelength-swept Fourier-domain mode-locked (FDML) laser still, to this day, enables highest imaging speeds through a very high-speed spectral tuning capability. The FDML laser achieves a tuning bandwidth of over 1/10th of its center wavelength and can sweep this entire bandwidth in less than a microsecond. Interestingly, even though it covers a very broad spectral range, instantaneously it has a narrow spectral linewidth that puts it in a unique space compared to other high-speed broadband laser sources, e.g., mode-locked lasers or supercontinuum sources. Although it has been applied for nonlinear Raman spectroscopy and imaging, a current drawback of this continuous wave laser is the relatively low instantaneous power of 10-100mW. Here, we report the combination of an FDML laser with a master oscillator power amplifier (MOPA) architecture to increase the instantaneous power of the FDML for nonlinear optical interactions. The output of an FDML laser around 1060nm is modulated to short pulses by using an electro-optic amplitude modulator and subsequently amplified using ytterbium-doped fiber amplifiers (YDFAs). This generates a spectral rainbow of 65 picosecond pulses, where each pulse has a distinct, monochromatic wavelength. The instantaneous power can be adjusted by the YDFAs to reach nonlinear optical excitation regimes. This wavelength-swept FDML-MOPA laser will have a vast range of applications in, e.g., nonlinear optics, spectroscopy, imaging, and sensing.

SiO2/Si(001) studied by time-resolved valence band photoemission at MHz repetition rates: Linear and nonlinear excitation of surface photovoltage

The authors investigate the fluence and doping dependence of the surface photovoltage (SPV) shifts at SiO2/Si(001) interfaces by time-resolved photoelectron spectroscopy. Charge carriers are excited by pumping photon energies of hνpump=1.2 and 2.4 eV and probed by high-order harmonics of hνprobe=22.6 eV at 0.2 and 0.7 MHz repetition rates. The authors observe SPV shifts of the nonbonding O2p state by 240 meV for SiO2/p-Si and by −140 meV for SiO2/n-Si upon pumping with hνpump=1.2 eV, and their decay rate is estimated from time-resolved measurements. Moreover, the authors observe a striking pumping fluence dependence of SPV at these interfaces, which indicates charge carrier generation by both linear and nonlinear optical excitations.

Anomalous Hall effect in semiconductor quantum wells in proximity to chiral p -wave superconductors

By using the gauge-invariant optical Bloch equation, we perform a microscopic kinetic investigation on the anomalous Hall effect in chiral p-wave superconducting states. Specifically, the intrinsic anomalous Hall conductivity in the absence of the magnetic field is zero as a consequence of Galilean invariance in our description. As for the extrinsic channel, a finite anomalous Hall current is obtained from the impurity scattering with the optically excited normal quasiparticle current even at zero temperature. From our kinetic description, it can be clearly seen that the excited normal quasiparticle current is due to an induced center-of-mass momentum of Cooper pairs through the acceleration driven by ac electric field. For the induced anomalous Hall current, we show that the conventional skew-scattering channel in the linear response makes the dominant contribution in the strong impurity interaction. In this case, our kinetic description as a supplementary viewpoint mostly confirms the results of Kubo formalism in the literature. Nevertheless, in the weak impurity interaction, this skew-scattering channel becomes marginal and we reveal that a novel induction channel from the Born contribution dominates the anomalous Hall current. This novel channel, which has long been overlooked in the literature, is due to the particle-hole asymmetry by nonlinear optical excitation. Finally, we study the case in the chiral p-wave superconducting state with a transverse conical magnetization, which breaks the Galilean invariance. In this situation, the intrinsic anomalous Hall conductivity is no longer zero. Comparison of this intrinsic channel with the extrinsic one from impurity scattering is addressed.

On the Performance of Hybrid Functionals for Non-linear Optical Properties and Electronic Excitations in Chiral Molecular Crystals: The Case of Butterfly-Shaped Dicinnamalacetone.

Purely organic chiral molecular assemblies in the solid state hold great potential for non-linear optical applications. Herein, a newly synthesised molecular system is reported, namely, dicinnamalacetone, an otherwise planar molecule that crystallises in a disordered non-centrosymmetric form with four different conformations having an overall predominance of a particular helicity. A combined experimental and theoretical approach, including single-crystal X-ray diffraction, Kurtz-Perry and ab initio methods, is employed to characterise the system and benchmark the performance of hybrid functionals for the prediction of non-linear optical properties and electronic excitations. Comparison of experiment and theory points to a particular set of hybrid functionals that provides an optimal description of this molecular system.

Intensity dependences of the nonlinear optical excitation of plasmons in graphene.

Recently, we demonstrated an all-optical coupling scheme for plasmons, which takes advantage of the intrinsic nonlinear optical response of graphene. Frequency mixing using free-space, visible light pulses generates surface plasmons in a planar graphene sample, where the phase matching condition can define both the wavevector and energy of surface waves and intraband transitions. Here, we also show that the plasmon generation process is strongly intensity-dependent, with resonance features washed out for absorbed pulse fluences greater than 0.1 J m-2 This implies a subtle interplay between the nonlinear generation process and sample heating. We discuss these effects in terms of a non-equilibrium charge distribution using a two-temperature model.This article is part of the themed issue 'New horizons for nanophotonics'.

Nonlinear optical corneal collagen crosslinking of ex vivo rabbit eyes

To determine whether riboflavin-induced collagen crosslinking (CXL) could be precisely achieved in the corneal stroma of exvivo rabbit eyes using nonlinear optical excitation with a low numerical aperture lens and enlarged focal volume. Gavin Herbert Eye Institute, University of California Irvine, Irvine, California, USA. Experimental study. The corneal epithelium was removed and the corneas were soaked in 0.5% riboflavin solution. Using a 0.1 numerical aperture objective, a theoretical excitation volume of 150μm×3μm was generated using 1W of 760nmfemtosecond laser light and raster scanned with 4.4μm line separation at varying effective speeds over a 4.50mm×2.25mm area. Corneal sections were examined for collagen autofluorescence. Collagen autofluorescence was enhanced 2.9 times compared with ultraviolet-A (UVA) CXL. Also, increasing speed was linearly associated with decreasing autofluorescence intensity. The slowest speed of 2.69mm/s showed a mean of 182.97μm±52.35 (SD) long autofluorescent scan lines axially in the central cornea compared with 147.84±4.35μm for UVA CXL. Decreasing dwell time was linearly associated with decreasing autofluorescence intensity, approaching that of UVA CXL at a speed of 8.9mm/s. Using an effective speed of 8.9mm/s, nonlinear optical CXL could be achieved over a 3.0mm diameter area in fewer than 4minutes.Further development of nonlinear optical CXL might result in safer, faster, and more effective CXL treatments. None of the authors has a financial or proprietary interest in any material or method mentioned.

Fluorescence excitation by enhanced plasmon upconversion under continuous wave illumination

We demonstrate effective background-free continuous wave nonlinear optical excitation of molecules that are sandwiched between asymmetrically constructed plasmonic gold nanoparticle clusters. We observe that near infrared photons are converted to visible photons through efficient plasmonic second harmonic generation. Our theoretical model and simulations demonstrate that Fano resonances may be responsible for being able to observe nonlinear conversion using a continuous wave light source. We show that nonlinearity enhancement of plasmonic nanostructures via coupled quantum mechanical oscillators such as molecules can be several orders larger as compared to their classical counterparts.

Nonlinear optical sub-bandgap excitation of ZnO-based photonic resonators

Zinc oxide (ZnO) is a versatile candidate for photonic devices due to its highly efficient optical emission. However, for pumping of ZnO photonic devices UV-sources are required. Here, we investigate the alternative usage of widely available pulsed near-infrared (NIR)-sources and compare the efficiency of linear and nonlinear excitation processes. We found that bulk ZnO, ZnO thin films grown by molecular beam epitaxy, and ZnO/SiO2 microdisk devices exhibit strong nonlinear response when excited with NIR pulses (λ ≈ 1060 nm). In addition, we show that the ZnO/SiO2 microdisks exhibit sharp whispering gallery modes over the blue-yellow part of the visible spectrum for both excitation conditions and high Q-factors up to Q = 4700. The results demonstrate that nonlinear excitation is an efficient way to pump ZnO photonic devices.

Tunable optical limiting optofluidic device filled with graphene oxide dispersion in ethanol.

An optofluidic device with tunable optical limiting property is proposed and demonstrated. The optofluidic device is designed for adjusting the concentration of graphene oxide (GO) in the ethanol solution and fabricated by photolithography technique. By controlling the flow rate ratio of the injection, the concentration of GO can be precisely adjusted so that the optical nonlinearity can be changed. The nonlinear optical properties and dynamic excitation relaxation of the GO/ethanol solution are investigated by using Z-scan and pump-probe measurements in the femtosecond regime within the 1.5 μm telecom band. The GO/ethanol solution presents ultrafast recovery time. Besides, the optical limiting property is in proportion to the concentration of the solution. Thus, the threshold power and the saturated power of the optical limiting property can be simply and efficiently manipulated by controlling the flow rate ratio of the injection. Furthermore, the amplitude regeneration is demonstrated by employing the proposed optofluidic device. The signal quality of intensity-impaired femtosecond pulse is significantly improved. The optofluidic device is compact and has long interaction length of optical field and nonlinear material. Heat can be dissipated in the solution and nonlinear material is isolated from other optical components, efficiently avoiding thermal damage and mechanical damage.

Optically enhanced coherent transport in YBa2Cu3O6.5 by ultrafast redistribution of interlayer coupling.

Nonlinear optical excitation of infrared active lattice vibrations has been shown to melt magnetic or orbital orders and to transform insulators into metals. In cuprates, this technique has been used to remove charge stripes and promote superconductivity, acting in a way opposite to static magnetic fields. Here, we show that excitation of large-amplitude apical oxygen distortions in the cuprate superconductor YBa2Cu3O6.5 promotes highly unconventional electronic properties. Below the superconducting transition temperature (Tc=50 K) inter-bilayer coherence is transiently enhanced at the expense of intra-bilayer coupling. Strikingly, even above Tc a qualitatively similar effect is observed up to room temperature, with transient inter-bilayer coherence emerging from the incoherent ground state and similar transfer of spectral weight from high to low frequency. These observations are compatible with previous reports of an inhomogeneous normal state that retains important properties of a superconductor, in which light may be melting competing orders or dynamically synchronizing the interlayer phase. The transient redistribution of coherence discussed here could lead to new strategies to enhance superconductivity in steady state.

Generation and Bistability of a Waveguide Nanoplasma Observed by Enhanced Extreme-Ultraviolet Fluorescence

We present a study of the highly nonlinear optical excitation of noble gases in tapered hollow waveguides using few-femtosecond laser pulses. The local plasmonic field enhancement induces the generation of a nanometric plasma, resulting in incoherent extreme-ultraviolet fluorescence from optical transitions of neutral and ionized xenon, argon, and neon. Despite sufficient intensity in the waveguide, high-order harmonic generation is not observed. The fluorescent emission exhibits a strong bistability manifest as an intensity hysteresis, giving strong indications for multistep collisional excitations.

Non-Linear Optical Microscopy Sheds Light on Cardiovascular Disease

Many cardiac diseases have been associated with increased fibrosis and changes in the organization of fibrillar collagen. The degree of fibrosis is routinely analyzed with invasive histological and immunohistochemical methods, giving a limited and qualitative understanding of the tissue's morphological adaptation to disease. Our aim is to quantitatively evaluate the increase in fibrosis by three-dimensional imaging of the collagen network in the myocardium using the non-linear optical microscopy techniques Two-Photon Excitation microscopy (TPE) and Second Harmonic signal Generation (SHG). No sample staining is needed because numerous endogenous fluorophores are excited by a two-photon mechanism and highly non-centrosymmetric structures such as collagen generate strong second harmonic signals. We propose for the first time a 3D quantitative analysis to carefully evaluate the increased fibrosis in tissue from a rat model of heart failure post myocardial infarction. We show how to measure changes in fibrosis from the backward SHG (BSHG) alone, as only backward-propagating SHG is accessible for true in vivo applications. A 5-fold increase in collagen I fibrosis is detected in the remote surviving myocardium measured 20 weeks after infarction. The spatial distribution is also shown to change markedly, providing insight into the morphology of disease progression.