Third-order Nonlinear Refraction Research Articles

Defect-controlled fabrication of reduced graphene oxide/ZnO/PMMA-based solid-state optical limiting filters with SA/RSA switching property

A solid-state optical limiting filter was fabricated by noncovalently functionalizing a graphene-based nanocomposite with a polymer. Graphene oxide was reduced by varying reducing agent concentration and functionalized with metal oxide nanoparticles to enhance electronic transitions and third-order nonlinear optical characteristics. The nanocomposite was dispersed over the PMMA polymer framework, and thin films with μm-scale thickness were fabricated using the dip coating method. XRD analysis confirmed the wurtzite crystal structure of ZnO nanoparticles and the amorphous nature of PMMA. The carbon structural integrity was analyzed using Raman spectra. Linear optical studies revealed a redshift in the π-π* transition peak in rGO, suggesting enhanced conjugation. Third-order nonlinear refraction and absorption properties were assessed using the Z-scan technique, revealing a switching behavior in nonlinear absorption at different input intensities. An increase in the relative concentration of sp2 domains enhanced the nonlinear absorption. Optical limiting potential, determined using open aperture Z-scan data, yielded a threshold value of 0.066 GW/cm2. This study aims to develop a solid-state optical filter with a high laser damage threshold by adjusting the reduction rate, tuning defect levels, and analyzing its effect on the optical limiting potential.

Novel polymorph of 2-amino-6-methyl pyridinium-4-methyl benzoate (2A6MP4MB) single crystals: Synthesis, crystal structure, optical, spectroscopic and self-defocusing capabilities for nonlinear optical applications

By using the slow evaporation solution growth technique, the 2-amino 6-methyl pyridinium 4-methyl benzoate (2A6MP4MB) is crystallized in a single, high-quality crystal. Single crystal X-ray diffraction (SXRD) was used to determine the crystal structure. The different functional groups of the substances were identified using Fourier Transform Infrared Spectroscopy (FTIR) analysis. The 2A6MP4MB crystal exhibits a significant optical transmittance throughout the complete visible spectrum and a lowered UV cutoff wavelength, according to studies conducted using UV-Vis spectrometers. The optical band gap energy (Eg) of a single crystal of 2A6MP4MB is 4.768[Formula: see text]eV. The compound’s photoluminescence (PL) spectrum in the title illustrates the green emission technique. We analyze the produced single crystal’s dielectric tensorial behavior at various frequencies. The produced 2A6MP4MB crystal’s third-order susceptibility, nonlinear refraction, and nonlinear absorption coefficient were evaluated using the [Formula: see text]-scan technique. A Vickers hardness tester was used to assess the created crystal’s mechanical stability.

Introducing Optical Nonlinearity in PDMS Using Organic Solvent Swelling

The feasibility of introducing optical nonlinearity in poly-dimethyl siloxane (PDMS) using organic solvent swelling was investigated. The third-order nonlinear refraction and absorption properties of the individual materials, as well as the PDMS/solvent compounds after swelling were characterized. The well-established Z-scan technique served as characterization method for the nonlinear properties under picosecond pulsed laser excitation at a 532 nm wavelength. These experiments included investigations on the organic solvents nitrobenzene, 2,6-lutidine, and toluene, which showed inherent optical nonlinearity. We showed that nitrobenzene, one of the most well-known nonlinear optical materials, has proven suboptimal in this context due to its limited swelling effect in PDMS and comparatively high (non)linear absorption, resulting in undesirable thermal effects and potential photo-induced damage in the composite material. Toluene and 2,6-lutidine not only exhibited lower absorption compared to nitrobenzene but also show a more pronounced swelling effect in PDMS. The incorporation of toluene caused a weight change of up to 116% of PDMS, resulting in substantial nonlinear optical effects, reflected in the nonlinear refractive index of the PDMS/toluene composite n2=3.1×10−15 cm2/W.

Saturable absorption and third-order nonlinear refraction of 2D CdSe nanoplatelets resonant with heavy-hole excitonic transitions

We report on the nonlinear optical response of CdSe nanoplatelets and CdSe/CdS core/shell nanoplatelets in the heavy-hole resonant excitonic transition spectral regions with femtosecond pulses. The nonlinear refraction and saturable absorption coefficients were obtained using the Z-scan technique, and the results were explained theoretically. The nonlinear optical response under nonresonant excitation has been previously examined; comparing with the results presented in this work, at least a one order of magnitude increase in the nonlinear refraction coefficient is evident.

Defect-mediated saturable absorption and carrier dynamics in tin (II) monosulfide quantum dots.

Tin (II) monosulfide (SnS) has attracted considerable attention in emerging photonics and optoelectronics because of high carrier mobility, large absorption coefficient, anisotropic linear and nonlinear optical properties, and long-time stability. In this Letter, we report third-order nonlinear absorption and refraction of SnS quantum dots (QDs). Under excitation with 800-nm femtosecond pulses, QDs exhibit saturable absorption (saturation intensity ∼ 47.69 GW/cm2) and positive refractive nonlinearity (nonlinear refraction coefficient ∼ 1.24 × 10-15 cm2/W). Nonetheless, we investigate charge carrier dynamics using femtosecond transient absorption spectroscopy and propose the presence of midgap defect states which not only dictate carrier dynamics but also give rise to nonlinear optical properties in SnS QDs.

The rich nonlinear optical responses in a squaraine derivative: Nonlinear absorption and transient nonlinear refraction dynamics

The abundant nonlinear optical responses of a squaraine derivative (2, 4-bis[4-(diethylamino)-2-hydroxyphenyl]squaraine, SQ-640) are explored at visible and near-infrared (NIR) regions. The sign and magnitude of the third-order (intensity depend) nonlinear absorption and refraction for SQ-640 are determined under different pluses with Z-scan method. The results of this work show reverse saturable absorption (RSA) of SQ-640 at visible and NIR region and its potential for optical limiting (OL) application. Moreover, SQ-640 shows self-focusing at visible wavelength while shows self-defocusing at NIR wavelengths. The transient refraction dynamics indicate that positive excited-state refraction causes self-focusing at visible region while negative nonlinear refraction at NIR region mainly originates from bound electron response (Kerr effect) and negative excited state refraction. Besides, the nonlinear refraction index of SQ-640 under 532 nm ranges from ∼ 10-19 m2/W at femtosecond pulses to ∼ 10-16 m2/W at nanosecond pulses and the second order hyperpolarizability is about 4 × 10-28 esu at nanosecond case. The Kerr refraction coefficient is about −6.54 × 10-19 m2/W at 700 nm under femtosecond laser pulses. The obtained OL thresholds at 532 nm are ∼ 26.8 mJ/cm2 for picosecond pulses and ∼ 85.6 mJ/cm2 for nanosecond pulses. The enriching information extracted from NLR in SQ-640 may offer an optional perspective to understand the structure–property relationships in these compounds. The results of optical nonlinearities in SQ-640 gained from this study may be of assistance to its better applications in laser protection and optical switching.

Synthesis, band gap structure and third order non-linear optical properties of zinc tungsten oxide nanocomposite using a single CW laser beam.

In this study, a composite of zinc tungsten oxide nanoparticles (W-ZnO NPs) has been synthesized via mixing Na2WO4 and zinc acetate in water, followed by dropwise addition of NaOH. The synthesized W-ZnO NPs were characterized using measurement methods such as XRD, dynamic light scattering (DLS), Scanning electron microscopy (SEM) and UV-Vis. Also, the results were compared with the pure synthesized ZnO and WO3 NPs. Non-linear optical properties of the synthesized composite were measured using the Z-scan technique with a continuous wave Nd-Yag laser. The negative non-linear absorption coefficient of the components was obtained which indicates that the saturation absorption occurred in this composite. In comparison with pure ZnO NPs, non-linear absorption decreases which can be attributed to the negligible optical response of WO3 structures. Also, the negative value of the close aperture Z-scan curve shows that the thermal lensing effect is the main reason for the third-order non-linear refraction.

Large third-order optical nonlinearities of two-dimensional CsPbBr3 nanoplatelets

Metal halide perovskites show considerable optical nonlinearity and could be used for cost-effective nonlinear optical devices if their nonlinear susceptibilities can be improved. Here, we report large optical nonlinearity, including third-order nonlinear absorption, refraction, and two-photon absorption excited luminescence, of CsPbBr3 nanoplatelets with a thickness of two or three atomic layers and a plane size of about 60 nm. Specifically, the nonlinear absorption was mainly induced by two-photon absorption at low incident powers, and the nonlinear absorption cross section reached 2.15 × 107 GM. It is two orders of magnitude larger than that of CsPbBr3 nanocrystals, which makes them an ideal optical limiting material. Furthermore, the nanoplatelets exhibited large self-phase modulation-induced nonlinear refraction, and the figures of merit W and T satisfied W >1 and T <1, which allow for optical switching. The large optical nonlinearity of CsPbBr3 nanoplatelets provides a basis for multifunctional applications in nonlinear optical devices.

Synthesis, crystal structure, characterization, Hirshfeld analysis, molecular docking and DFT calculations of 5-Phenylamino-isophthalic acid: A good NLO material

5-Phenylamino-isophthalic acid (H2L) (C15H13NO4) has been synthesized, characterized via single-crystal X-ray diffraction, spectroscopic techniques and also studied theoretically using DFT approach. The compound crystallizes in a monoclinic crystal system with a P21/c space group with Z = 2 and the following unit cell dimensions: a = 10.4415(14) Å, b = 16.472(2) Å, c = 7.5305(10) Å. DFT calculations were carried out by B3LYP/6–311++G(d,p) level and geometry optimization, vibrational analysis, MEP, ELF, NBO, NHO, and FMO analysis were also carried out. The calculated values showed excellent agreement with the experimental data. The vibrational frequencies were evaluated using density functional theory (DFT) with the complete PED analysis. The Molecular Frontiers Orbitals (FMO) or HOMO/LUMO energy values showed that there wasa satisfying interchange of charge occurring within the molecule. Hirshfeld surface analysis was carried out to study 3-D and 2-D interactions in crystal. Molecular docking was done with 4 protein receptors to find the best ligand-protein interactions. The nonlinear optical characteristics of the title compound have been evaluated using the Z-scan method with CW diode laser working at 520 nm. The third-order nonlinear refraction coefficient (n2), nonlinear absorption (β), nonlinear susceptibility χ(3), and second-order hyperpolarizability (γ) are of the order of 10−8 cm2/ W, 10−3 cm/ W, 10−7 esu, and 10−27 esu, respectively.

Synthesis, characterization, and femtosecond third-order optical nonlinearity of Au@Ag core–shell nanoparticles

In this work, the Au@Ag bimetallic core–shell nanostructures were synthesized by a seed-mediated growth. The crystal structure, morphology, elemental composition, atomic concentration, and absorption spectrum of the as-synthesized nanoparticles were characterized by means of X-ray diffraction, transmission electron microscopy, energy dispersive spectroscopy, X-ray photoelectron spectroscopy, and ultraviolet–visible linear absorption spectrum, respectively. The femtosecond third-order optical nonlinearities of nanoparticle dispersions were investigated by carrying out the femtosecond-pulsed [Formula: see text]-scan measurements at 800[Formula: see text]nm. The experimental results indicate that Au@Ag core–shell nanoparticles exhibit the positive refractive nonlinearity and negative absorptive nonlinearity. The third-order nonlinear refraction indexes of Au and Au@Ag nanoparticles are measured to be [Formula: see text] and [Formula: see text][Formula: see text]cm2/GW, respectively. The results show that the bimetallic nanoparticle has potential possibility in nonlinear photonic applications.

Transformation from Self-Focusing to Self-Defocusing of Silver Nanoparticles.

The nonlinear refraction of silver nanoparticles (AgNPs) in n-hexane was studied by using the closed-aperture Z-scan technique with a 532 nm nanosecond laser. It was found that, the nonlinear refraction of AgNPs shows the coexistence and transformation from self-focusing to self-defocusing. Specifically, self-focusing occurs at low excitation intensity, self-defocusing occurs at high excitation intensity, and coexistence of self-focusing and self-defocusing occurs at relatively moderate excitation intensity. The experimental results were analysed and discussed in terms of third-order and fifth-order nonlinear refractive effect. Specifically, the self-focusing is caused by the positive third-order nonlinear refraction, the self-defocusing is induced by the negative fifth-order nonlinear refraction, and the transformation from the self-focusing to self-defocusing at medium excitation intensity is caused by the competition of third-order and fifth-order nonlinear refraction. Finally, the third-order refractive index and fifth-order refractive index were obtained.

Multiphoton absorption and dispersive nonlinear refraction of ZnO in VIS-NIR bands

Zinc oxide (ZnO), as one of the third-generation semiconductor materials, has attracted extensive research interest, but its nonlinear optical properties in near-infrared (NIR) band are rarely involved. Herein, the beam propagation diffraction model has been extended to handle up to the 9th-order optical nonlinearity, and still has excellent performance of fitting experimental data. Multiphoton absorption effects were experimentally investigated by z-scan measurement in visible (VIS)-NIR bands. In an N-photon absorption (N-PA) spectral regime, the respective N-PA effect dominates nonlinear absorption, while all other orders are negligible under the experimental laser intensities. In VIS-NIR bands, only the third-order nonlinear refraction is significant for Kerr nonlinear refractive index, while the higher orders can be ignored. The nonlinear figure of merit is low due to the strong 2PA effect in VIS band, but increases by an order of magnitude, up to a maximum value of 5.8, in the spectral region where the 2PA effect diminishes. These results indicate that ZnO is a valuable candidate for nonlinear photonics applications in a broad NIR band accommodating telecom wavelength.

Aggregation Induced Emission and Nonlinear Optical Properties of an Intramolecular Charge-Transfer Compound.

Intramolecular charge transfer (ICT) compounds have attracted wide attention for their potential applications in optoelectronic materials and devices such as fluorescent sensors, dye-sensitized solar cells, organic light emitting diodes and nonlinear optics. In this work, we have synthesized a new ICT compound, dimethyl-[4-(7-nitro-benzo[1,2,5]thiadiazol-4-yl)-phenyl]-amine (BTN), and have fabricated it into low dimensional micro/nano structures with well-defined morphologies. These self-assembled nanostructures exhibit high efficiency solid state fluorescence via an aggregation induced emission mechanism, which overcomes the defect of fluorescence quenching caused by aggregation in the solid state of traditional luminescent materials. We also explored and studied the nonlinear optical properties of this material through the Z-scan method, and found that this material exhibits large third-order nonlinear absorption and refraction coefficients, which promises applications of the materials in the fields of nonlinear optics and optoelectronics.

Preparation of Ag@ZnO core–shell nanostructures by liquid-phase laser ablation and investigation of their femtosecond nonlinear optical properties

Ag@ZnO core–shell nanostructures, ZnO nanoparticles (NPs), and Ag NPs were synthesized by laser ablation in water using 8 ns, 1064 nm, and 50 mJ/pulse. The structural, morphological, componential, and optical properties of as-synthesized NPs were examined by X-ray diffraction, transmission electron microscopy, electron diffraction spectrum, and ultraviolet–visible absorption, respectively. The third-order nonlinear optical properties of aqueous dispersions of three NPs were characterized by performing Z-scan experiments with femtosecond laser pulses at 800 nm. It is shown that three NPs exhibit the positive refractive nonlinearity in the absence of nonlinear absorption and the third-order nonlinear refraction index increases in the order of NPs ZnO < Ag < Ag@ZnO. The results indicate that the Ag@ZnO core–shell nanostructure is a promising candidate for applications in ultrafast all-optical switching.

Structure-changed third-order optical nonlinearity in CaCu3Ti4O12 thin films grown on MgO(111) substrates

CaCu3Ti4O12 (CCTO) thin films of preference (220) orientation are deposited on MgO(111) substrates using pulsed laser deposition method. The third-order optical nonlinearity of CCTO films was investigated using Z-scan technique at a wavelength of 532 nm with 25 ps duration pulses. The self-focusing behavior in CCTO films was observed, which is different from the traditional CCTO films grown on LaAlO3 (0001), MgO(100), and fused silica substrates of self-defocusing behavior. The third-order nonlinear refraction coefficient is determined of a value 0.76 cm2/GW, along with the fifth-order nonlinear refractive index -0.2 cm4/GW2, the nonlinear absorption coefficient -1.87 × 10−7 m/W and saturable absorption intensity 1.72 GW/cm2. The structure-changed nonlinear refraction and fast response at picosecond time-domain extend the potential applications of CaCu3Ti4O12 thin films for nonlinear photonics devices.

Third order nonlinear optical properties of gold/alumina multilayer nanocomposites with different nanoparticle arrangements

The linear and nonlinear optical properties of gold nanoparticle/alumina matrix multilayer nanocomposites obtained by successive laser deposition were studied. The nonlinear optical properties of the gold nanoparticle layers embedded in alumina were determined by Z-scan at 532 nm, using a picosecond pulse laser. The linear absorption, third-order nonlinear absorption and refraction were found to depend on the arrangement of gold nanoparticles in the nanocomposite thin film, when essential characteristics such as nanoparticle dimension, metal concentration and total film thickness are constant. When partial self-correlation between gold nanoparticles in successive layers occurs, in the case of thin alumina layers, linear and nonlinear optical properties of the nanocomposites are enhanced, reaching values of -2.8 × 10−6 m/W and 1.6 × 10−13 m2/W for the third-order nonlinear absorption and refraction coefficients, respectively.

Ultrafast nonlinear refraction measurements of infrared transmitting materials in the mid-wave infrared.

We utilize the conventional Z-scan technique to provide absolute measurements of third-order nonlinear refraction coefficients (n2) in the mid-wave infrared at 2 µm and 3.9 µm of common optical materials that have transparency windows spanning this regime. We study a variety of narrow band gap and wide band gap semiconductors, fluoride crystals (BaF2, CaF2, LiF, and MgF2) and optical glasses, and a series of chalcogenide glasses. The n2 is found to span on the order of ∼10-15 to ∼10-12 cm2/W for the semiconductors, ∼10-16 cm2/W for the fluoride crystals and glasses, and ∼10-14 to ∼10-13 cm2/W for the chalcogenides. The experimental results are compared to previous measurements of n2 conducted in the visible and near-infrared along with empirical and theoretical formulations.

A Seedless Method for Gold Nanoparticle Growth inside a Silica Matrix: Fabrication of Materials Capable of Third-Harmonic Generation in the Near-Infrared.

A composite in which gold nanoparticles (AuNPs) approximately 10 nm in size are embedded in amorphous transparent silica matrix has been produced. The synthetic protocol uses HAuCl4 as the Au ion source, tetraethoxysilane (TEOS) as the SiO2 precursor, and l-ascorbic acid (AA) as the reducing agent. AA is employed before the sol-gel process in an amount sufficient only for reduction of Au3+ ions to Au+ . By using a cationic surfactant, benzylcetyldimethylammonium chloride hydrate (BDAC) and/or cetyltrimethylammonium bromide (CTAB), the Au+ ions are encapsulated within metalomicelles, which prevents them from being reduced to Au0 and enables their homogeneous distribution in the gel. Reduction of Au+ to Au0 and the growth of the AuNPs occurs at room temperature during the gelation, and arises from the release of EtOH during the hydrolysis of TEOS. The composites contain 0.027 wt % of Au. They exhibit nonlinear optical behavior characterized by the third-order nonlinear refraction index, n2 , in the range 3.6-5.7×10-16 cm2 W-1 at λ=1.030 μm. The composites are capable of effective third-harmonic generation of ultrashort near-IR (210 fs, 1.030 μm) laser pulse through a direct third-order mechanism.

Anisotropic nonlinear Kerr media: Z-scan characterization and interaction with hybridly polarized beams.

The interaction of intense laser with matter gives rise to a variety of novel nonlinear optical effects, reflects the nonlinear optical property of a material, and modulates the light propagation behavior. Herein, we investigate anisotropic Kerr nonlinearities induced by both scalar and vectorial optical fields. Firstly, we present the anisotropic third-order nonlinear refraction indexes related to left-hand and right-hand components, which depend on the ellipticity, the dichroism coefficient, the anisotropy coefficient, as well as the crystal orientation angle. Secondly, we develop the elliptically polarized light Z-scan technique for characterizing third-order nonlinear susceptibility tensor in anisotropic nonlinear Kerr media, which is demonstrated experimentally. Lastly, with the known nonlinear optical parameters, we numerically study both the vectorial self-diffraction behaviors and spin angular momentum (SAM) characteristics of hybridly polarized beams induced by an anisotropic Kerr nonlinearity. It is shown that the anisotropic Kerr nonlinearity offers a new approach to manipulate the polarization-structured light field, which has potential applications in SAM manipulation, three-dimensional crystal orientation, and polarization-sensitive detection and sensing.

Absolute Nonlinear Refractive Index Spectra Determination of Organic Molecules in Solutions.

It has been a great challenge to measure the spectrum of pure bound-electronic third-order nonlinear refraction ( n2) of organic chromophores in solutions because of the spurious contribution from the solvent and cuvette walls. In order to circumvent this problem, we present here a new method to obtain a highly accurate absolute n2 value of organic molecules in solutions with a self-referenced nonlinear ellipse rotation (NER) technique. As a proof of concept, we measured n2 spectra of two well-known chromophores, rhodamines B and 6G dissolved in methanol, in the range from ∼600 to 1200 nm. Our results pointed out that these two dyes present similar dispersion curves with strong negative nonlinearities near the one-photon absorption band and small positive values at long wavelengths. Furthermore, the negative signal of the dyes can be strong enough to cancel and even invert the positive nonlinear refraction of the solvent (methanol) as the solution's concentration increases. To understand the n2 spectrum and its connection to molecular properties of organic chromophores, we employed the sum-over-states (SOS) approach within the few-energy-level model and observed an excellent agreement between the experimental and theoretical spectra. In this way, we believe that, employing our NER technique and the SOS model, it is possible to determine both experimentally and theoretically the absolute magnitude and spectra of pure electronic n2 for a large variety of other organic molecules.