Synthesis, Physicochemical and Third Order Nonlinear Optical Properties of Bis-Chalcone (BBDP) as Donor-pi Acceptor Chromophore in Organize Medium.

Bis-Chalcone (BBDP) has been prepared by condensation of N, N-dimethyl benzaldehyde and 1,1'-([1,1'-biphenyl]-4,4'-diyl) di (ethan-1-one), and structure of BBDP was characterized by Mass Spectra, 13C-NMR, 1H-NMR, and IR. Physicochemical properties including Dipole-moments, Stoke-Shifts, Oscillator-strength, dielectric constant and quantum-yields of fluorescence of BBDP were investigated by the emission and absorbances in different solvents. Compound (BBDP) displayed bathochromic shift upon increasing the solvent polarity (from n-Hexane to DMSO). Furthermore, we have exploited third-order nonlinear optical characteristics of the bisChalone were invigilated by the Z-scan techniques in Chloroform. The measurements were taken with a continuous-wave (CW) diode laser having a wavelength of 520 nm in CHCl3 solvent. The third-order nonlinear optical properties, such as the nonlinear refractive index (NLRI) n2, nonlinear absorption coefficient (NLAC) ß, and nonlinear susceptibility χ(3), were measured at various solution concentrations and laser powers. The obtained values of n2, ß, and χ(3) were estimated to be high, of the order of 10-7(cm2/W), 10-3 (cm/W), and 10-6 (esu), respectively. As a result, bis-chalcone (BBDP) is considered as a promising candidate for applications in nonlinear optical (NLO) devices and optical limiting (OL).

Excellent ultraviolet optical limiting properties of Se nanosheets.

Selenium (Se) is located in the fourth period of the periodic table in group VIA (element 34). In this experiment, three different solvents (isopropyl alcohol, N-methyl-2-pyrrolidone, and ethanol) were used to prepare the two-dimensional Se nanosheets, which were manufactured by the liquid phase exfoliation method with a thickness of 3.35-4.64 nm and a transverse scale of several hundred nanometers. The nonlinear absorption properties at 355, 532, and 1064 nm were studied using the open apertureZ-scan technique. Final results showed that Se nanosheets exhibited optical limiting (OL) effect in all three wavebands and three solvents, and had large two-photon absorption coefficients, especially in ultraviolet (UV) waveband. Which proved that Se nanosheets had great potential application as excellent OL materials in UV waveband. Our research broadens the path for the semiconductor field of Se, inspires the application of Se in nonlinear optics field.

Fabrication, Characterization of Basic Blue 7 Dye-Doped PVA Films and Their Third-Order Nonlinear Optical Properties.

In this work, we report on the fabrication, characterization and the third-order nonlinear optical (NLO) properties of basic blue 7 (BB 7) dye‒doped polyvinyl alcohol (PVA) polymer thin films. The absorption spectra of BB 7 dye‒PVA films were measured by UV‒visible absorption studies. The functional groups of BB 7‒PVA films have been identified by FT‒IR spectroscopic analysis. The surface morphology was examined by AFM and SEM analysis which shows that the BB 7 dye‒doped PVA films have a homogenous and smooth surface. The nonlinear absorption and refraction of BB 7‒PVA films were respectively explored by open aperture and closed aperture Z‒scan technique using a 5 mW semiconductor diode laser of 635 nm wavelengths. The BB 7‒PVA films exhibit the reverse saturable absorption (RSA) and self-defocusing effect and the measured third‒order nonlinear susceptibility χ(3) values of these films were found to be of the order of 10- 5 esu. The present experimental results show that BB 7‒PVA films may have potential applications in future photonic and NLO devices.

Nonlinear absorption-based analysis of energy deposition in melanosomes for 532-nm short-pulsed laser skin treatment.

BACKGROUND AND OBJECTIVES: The clinical use of 532-nm short-pulsed lasers has provided effective treatment of epidermal pigmented lesions. However, the detection of significant differences in treatment effects between picosecond and nanosecond lasers has still varied among clinical studies. For robust evaluation of the differences based on the treatment mechanism, this study presents a nonlinear absorption-based analysis of energy deposition in melanosomes for 532-nm short-pulsed laser treatment. STUDY DESIGN/MATERIALS AND METHODS: Nonlinear absorption by melanin is modeled based on sequential two-photon absorption. Absorption cross-sections and nonradiative lifetimes of melanin, which are necessary for the nonlinear absorption-based analysis, are determined from transmittance measurement. Using the model and parameters, energy deposition in melanosomes was calculated with varying fluence and pulse width settings, including actual clinical parameters. RESULTS: The energy deposition in melanosomes increased with shorter laser pulses, and subnanosecond laser pulses were found to be most efficient. The comparison of energy deposition calculated using clinical parameters demonstrated the differences in treatment effects between picosecond and nanosecond lasers reported in clinical studies. CONCLUSION: The nonlinear absorption-based analysis provides quantitative evidence for the safety and efficacy evaluation of short-pulsed laser treatments, which may lead to the establishment of numerical indices for determining treatment conditions. Future studies considering the effects of the surrounding tissue on energy deposition in melanosomes will be needed.

Siloxene Nanosheets and Their Hybrid Gel Glasses for Broad-Band Optical Limiting.

With the development of laser technology, the research of novel laser protection materials is of great significance. In this work, dispersible siloxene nanosheets (SiNSs) with a thickness of about 1.5 nm are prepared by the top-down topological reaction method. Based on the Z-scan and optical limiting testing under the visible-near IR ranges nanosecond laser, the broad-band nonlinear optical properties of the SiNSs and their hybrid gel glasses are investigated. The results show that the SiNSs have outstanding nonlinear optical properties. Meanwhile, the SiNSs hybrid gel glasses also exhibit high transmittance and excellent optical limiting capabilities. It demonstrates that SiNSs are promising materials for broad-band nonlinear optical limiting and even have potential applications in optoelectronics.

Record Aluminum Molecular Rings for Optical Limiting and Nonlinear Optics.

Crystalline cluster materials, a class of functional motif aggregations, provide a great opportunity for tuning the properties stemming from the flexible and accurate variation of inorganic and organic compositions. In this study, we demonstrate the effects of functional ligand and ring size regulation on the structures and third-order nonlinear optical (NLO) properties. Revealed by the single-crystal X-ray analysis results, aluminum molecular ring expansion is achieved by 2×9 and 3×6 strategies. In terms of the given organic shells, we further tuned the aluminum molecular ring sizes from 3.0 nm to 1.7 nm. The picosecond Z-scan measurements results revealed that the third-order NLO performances do not only depend on the general conjugate interactions but are also related to hydrogen bonding, polarizability, and ring sizes. The large nonlinear absorption coefficient and onset prove that the observed samples are promising candidates for the field of nonlinear optics.

Looking beyond the Surface: The Band Gap of Bulk Methylammonium Lead Iodide.

Despite the intense research on photovoltaic lead halide perovskites, reported optical properties as basic as the absorption onset and the optical band gap vary significantly. To unambiguously answer the question whether the discrepancies are a result of differences between bulk and "near-surface" material, we perform two nonlinear spectroscopies with drastically different information depths on single crystals of the prototypical (CH3NH3)PbI3 methylammonium lead iodide. Two-photon absorption, detected via the resulting generation of carriers and photocurrents (2PI-PC), probes the interband transitions with an information depth in the millimeter range relevant for bulk (single-crystal) material. In contrast, the transient magneto-optical Kerr effect (trMOKE) measured in a reflection geometry determines the excitonic transition energies in the region near (hundreds of nm) the surface which also determine the optical properties in typical thin films. To identify differences between structural phases, we sweep the sample temperature across the orthorhombic-tetragonal phase transition temperature. In the application-relevant room-temperature tetragonal phase (at 170 K), we find a bulk band gap of 1.55 ± 0.01 eV, whereas in the near-surface region excitonic transitions occur at 1.59 ± 0.01 eV. The latter value is consistent with previous reflectance measurements by other groups and considerably higher than the bulk band gap. The small band gap of the bulk material explains the extended infrared absorption of crystalline perovskite solar cells, the low-energy bands which carry optically driven spin-polarized currents, and the narrow bandwidth of crystalline perovskite photodetectors making use of the spectral filtering at the surface.

Evidence of Band-Edge Hole Levels Inversion in Spherical CuInS2 Quantum Dots.

CuInS2 (CIS) quantum dots (QDs) have emerged as one of the most promising candidates for application in a number of new technologies, mostly due to their heavy-metal-free composition and their unique optical properties. Among those, the large Stokes shift and the long-lived excited state are the most striking ones. Although these properties are important, the physical mechanism that originates them is still under debate. Here, we use two-photon absorption spectroscopy and ultrafast dynamics studies to investigate the physical origin of those phenomena. From the two-photon absorption spectroscopy, we observe yet another unique property of CIS QDs, a two-photon absorption transition below the one-photon absorption band edge, which has never been observed before for any other semiconductor nanostructure. This originates from the inversion of the 1S and 1P hole level order at the top of the valence band and results in a blue-shift of the experimentally measured one photon absorption edge by nearly 100 to 200 meV. However, this shift is not large enough to account for the Stokes shift observed, 200-500 meV. Consequently, despite the existence of the below band gap optical transition, photoluminescence in CIS QDs must originate from trap sites. These conclusions are reinforced by the multiexciton dynamics studies. From those, we demonstrate that biexciton Auger recombination behaves similarly to negative trion dynamics on these nanomaterials, which suggests that the trap state is an electron donating site.

Enhanced Ultrafast Nonlinear Optical Response in Ferrite Core/Shell Nanostructures with Excellent Optical Limiting Performance.

Nonlinear optical nanostructured materials are gaining increased interest as optical limiters for various applications, although many of them suffer from reduced efficiencies at high-light fluences due to photoinduced deterioration. The nonlinear optical properties of ferrite core/shell nanoparticles showing their robustness for ultrafast optical limiting applications are reported. At 100 fs ultrashort laser pulses the effective two-photon absorption (2PA) coefficient shows a nonmonotonic dependence on the shell thickness, with a maximum value obtained for thin shells. In view of the local electric field confinement, this indicates that core/shell is an advantageous morphology to improve the nonlinear optical parameters, exhibiting excellent optical limiting performance with effective 2PA coefficients in the range of 10-12 cm W-1 (100 fs excitation), and optical limiting threshold fluences in the range of 1.7 J cm-2 . These values are comparable to or better than most of the recently reported optical limiting materials. The quality of the open aperture Z-scan data recorded from repeat measurements at intensities as high as 35 TW cm-2 , indicates their considerably high optical damage thresholds in a toluene dispersion, ensuring their robustness in practical applications. Thus, the high photostability combined with the remarkable nonlinear optical properties makes these nanoparticles excellent candidates for ultrafast optical limiting applications.

Z-Scan and Absorption Study of Crocin and Rhodamine B Decolorization by Bacterial Laccase.

Dye decolorization is currently measured by the reduction of dye absorption, based on its linear optical properties in solution. However, this method is not suitable for high dye concentrations with linear attributes in the absorption spectra. In this work, nonlinear optical properties are used to study dye decolorization of Crocin and Rhodamine B treated with a bacterial laccase. For this purpose, the Z-scan was used to obtain the nonlinear refractive indices and nonlinear absorption coefficient of Rhodamine B and Crocin in the presence and absence of the bacterial laccase enzyme. The results showed that nonlinear optical properties could be used to study dye decolorization in solutions.

Nonlinear Absorption and Low-Threshold Multiphoton Pumped Stimulated Emission from All-Inorganic Perovskite Nanocrystals.

Halide perovskite materials have attracted intense research interest due to the striking performance in photoharvesting photovoltaics as well as photoemitting applications. Very recently, the emerging CsPbX3 (X = Cl, Br, I) perovskite nanocrystals have been demonstrated to be efficient emitters with photoluminescence quantum yield as high as ∼90%, room temperature single photon sources, and favorable lasing materials. Herein, the nonlinear optical properties, in particular, the multiphoton absorption and resultant photoluminescence of the CsPbBr3 nanocrystals, were investigated. Notably, a large two-photon absorption cross-section of up to ∼1.2 × 10(5) GM is determined for 9 nm sized CsPbBr3 nanocrystals. Moreover, low-threshold frequency-upconverted stimulated emission by two-photon absorption was observed from the thin film of close-packed CsPbBr3 nanocrystals. The stimulated emission is found to be photostable and wavelength-tunable. We further realize the three-photon pumped stimulated emission in green spectra range from colloidal nanocrystals for the first time. Our results reveal the strong nonlinear absorption in the emerging CsPbX3 perovskite nanocrystals and suggest these nanocrystals as attractive multiphoton pumped optical gain media, which would offer new opportunities in nonlinear photonics and revive the nonlinear optical devices.

Broadband Two-Photon Absorption Characteristics of Highly Photostable Fluorenyl-Dicyanoethylenylated [60]Fullerene Dyads.

We synthesized four C60-(light-harvesting antenna) dyads C60 (>CPAF-Cn) (n = 4, 9, 12, or 18) 1-Cn for the investigation of their broadband nonlinear absorption effect. Since we have previously demonstrated their high function as two-photon absorption (2PA) materials at 1000 nm, a different 2PA wavelength of 780 nm was applied in the study. The combined data taken at two different wavelength ranges substantiated the broadband characteristics of 1-Cn. We proposed that the observed broadband absorptions may be attributed by a partial π-conjugation between the C60 > cage and CPAF-Cn moieties, via endinitrile tautomeric resonance, giving a resonance state with enhanced molecular conjugation. This transient state could increase its 2PA and excited-state absorption at 800 nm. In addition, a trend of concentration-dependent 2PA cross-section (σ2 ) and excited-state absorption magnitude was detected showing a higher σ value at a lower concentration that was correlated to increasing molecular separation with less aggregation for dyads C60(>CPAF-C18) and C60(>CPAF-C9), as better 2PA and excited-state absorbers.

Ultrahigh Nonlinear Responses from MXene Plasmons in the Short-Wave Infrared Range.

Surface plasmons in 2D materials such as graphene exhibit exceptional field confinement. However, the low electron density of majority of 2D materials, which are semiconductors or semimetals, has limited their plasmons to mid-wave or long-wave infrared regime. This study demonstrates that a 2D Ti3C2Tx MXene with high electron density can not only support strong plasmon confinement with an acoustic plasmon mode in the short-wave infrared region, but also provide ultrahigh nonlinear responses. The acoustic MXene plasmons (AMPs) in the MXene (Ti3C2Tx)-insulator (SiO2)-metal (Au) nanostructure generate in the 1.5-6.0 µm wavelength range, exhibiting a two orders of magnitude reduction in wavelength compared to wavelength in free space. Furthermore, AMP resonators with patterned Au rods exhibit a record-high nonlinear absorption coefficient of 1.37 × 10-2 m W-1 at wavelength of 1.56 µm, ≈3 orders of magnitude greater than the highest value recorded for other 2D materials. These results indicate that MXenes can overcome fundamental plasmon wavelength limitations of previously studied 2D materials, providing groundbreaking opportunities in nonlinear optical applications, including all-optical processing and ultrafast optical switching.

NLO response of photoswitchable azobenzene-based materials.

The nonlinear optical (NLO) response of three π-conjugated azobenzene (AB) derivatives was investigated under picosecond laser excitation by means of the Z-scan technique to evaluate the effect of an ethynyl-based conjugated spacer on the NLO properties of ABs. All modules possessed large third-order nonlinearity, but unexpectedly it was the less extended AB derivative that exhibited the largest NLO response. This finding has been confirmed by means of DFT calculations and was attributed to a higher cis/trans ratio of the particular AB derivative in its investigated photoequilibrated state. Furthermore, the influence of the amount of cis isomer on the third-order nonlinear susceptibility [χ((3))] of the less extended AB derivative has been thoroughly investigated. Specifically, modulation of the NLO response has been successfully achieved by tuning the isomeric composition of the investigated photostationary state. These results highlighted the cis-dependent increase of the NLO response to support the general idea that such compounds can be used for multistep switching NLO materials.

Two-photon absorption in colloidal semiconductor nanocrystals: a review.

Large two-photon absorption (2PA) cross-section combined with high emission quantum efficiency and size-tunable bandgap energy has put colloidal semiconductor nanocrystals (NCs) on the vanguard of nonlinear optical materials. After nearly two decades of intense studies on the nonlinear optical response in quantum-confined semiconductors, this is still a vibrant field, as novel nanomaterials are being developed and new applications are being proposed. In this review, we examine the progress of 2PA research in NCs, highlighting the impact of quantum confinement on the magnitude and spectral characteristics of this nonlinear response in semiconductor materials. We show that for NCs with three-dimensional quantum confinement, the so-called quantum dots, 2PA cross-section grows linearly with the nanoparticle volume, following a universal volume scaling. We overview strategies used to gain further control over the nonlinear optical response in these structures by shape and heterostructure engineering and some applications that might take advantage of the series of unique properties of these nanostructures.

Investigations on the Nonlinear Optical Properties of 0D, 1D, and 2D Boron Nitride Nanomaterials in the Visible Spectral Region.

In recent years, boron nitride nanomaterials have attracted increasing attention due to their unique properties such as high temperature stability and high thermal conductivity. They are structurally analogous to carbon nanomaterials and can also be generated as zero-dimensional nanoparticles and fullerenes, one-dimensional nanotubes and nanoribbons, and two-dimensional nanosheets or platelets. In contrast to carbon-based nanomaterials, which have been extensively studied during recent years, the optical limiting properties of boron nitride nanomaterials have hardly been analysed so far. This work summarises a comprehensive study on the nonlinear optical response of dispersed boron nitride nanotubes, boron nitride nanoplatelets, and boron nitride nanoparticles using nanosecond laser pulses at 532 nm. Their optical limiting behaviour is characterised by means of nonlinear transmittance and scattered energy measurements and a beam profiling camera is used to analyse the beam characteristics of the transmitted laser radiation. Our results show that nonlinear scattering dominates the OL performance of all measured boron nitride nanomaterials. Boron nitride nanotubes show a large optical limiting effect, much stronger than the benchmark material, multi-walled carbon nanotubes, which makes them promising for laser protection applications.

Polarization Z-Scan Studies Revealing Plasmon Coupling Enhancement Due to Dimer Formation of Gold Nanoparticles in Nematic Liquid Crystals.

We investigate the plasmon coupling of gold nanoparticle (AuNP) dimers dispersed in a nematic liquid crystal matrix using the polarization z-scan technique. Our experimental setup includes the precise control of incident light polarization through polarization angles of 0°, 45°, and 90°. Two distinct cell orientations are examined: parallel and twisted nematic cells. In parallel-oriented cells, where liquid crystal molecules and AuNPs align with the rubbing direction, we observe a remarkable 2-3-fold increase in the nonlinear absorption coefficient when the polarization of the incident light is parallel to the rubbing direction. Additionally, a linear decrease in the third-order nonlinear absorption coefficient is noted as the polarization angle varies from 0° to 90°. In the case of twisted nematic cells, the NPs do not have any preferred orientation, and the enhancement remains consistent across all polarization angles. These findings conclusively establish that the observed enhancement in the nonlinear absorption coefficient is a direct consequence of plasmon coupling, shedding light on the intricate interplay between plasmonic nanostructures and liquid crystal matrices.

Cubic Nonlinearity of Graphene-Oxide Monolayer.

The cubic nonlinearity of a graphene-oxide monolayer was characterized through open and closed z-scan experiments, using a nano-second laser operating at a 10 Hz repetition rate and featuring a Gaussian spatial beam profile. The open z-scan revealed a reverse saturable absorption, indicating a positive nonlinear absorption coefficient, while the closed z-scan displayed valley-peak traces, indicative of positive nonlinear refraction. This observation suggests that, under the given excitation wavelength, a two-photon or two-step excitation process occurs due to the increased absorption in both the lower visible and upper UV wavelength regions. This finding implies that graphene oxide exhibits a higher excited-state absorption cross-section compared to its ground state. The resulting nonlinear absorption and nonlinear refraction coefficients were estimated to be approximately ~2.62 × 10-8 m/W and 3.9 × 10-15 m2/W, respectively. Additionally, this study sheds light on the interplay between nonlinear absorption and nonlinear refraction traces, providing valuable insights into the material's optical properties.

Synthesis, Linear and Nonlinear Optical Properties of Ag/Al2O3 Nanocomposites.

This work reports a detailed study of the synthesis, characterization and third-order nonlinear optical properties of Ag and Al2O3 nanoparticles and their polymer nanocomposites. Ag and Al2O3 nanoparticles were prepared by the chemical precipitation method. The X-ray diffraction studies confirmed the purity and the crystalline nature of the sample and revealed the crystallite size. The linear optical properties and the structural morphology of the nanoparticles were confirmed using UV-visible spectroscopy and SEM analysis. The prepared nanoparticles were introduced into the polymer matrix by the spin-coating technique. Open-aperture and closed-aperture Z-scan technique was used to study the nonlinear absorption and nonlinear refraction of the samples under a Q-switched Nd:YAG laser at 532 nm. The observed third-order nonlinear optical susceptibility (χ(3)) was on the order of 10-6 esu, which indicates that these materials are potential candidates for photonic applications.

Femtosecond Laser-Induced Anisotropic Structure and Nonlinear Optical Response of Yttria-Stabilized Zirconia Single Crystals with Different Planes.

Nonlinear optical properties have been extensively studied due to their promising nonlinear effects and various applications. With ultrashort duration and ultrahigh intensity, a femtosecond laser can fabricate various superior-quality micro-/nanostructures to improve the nonlinearity of materials, which are promising for stable and high-performance nonlinear devices. In this contribution, yttria-stabilized zirconia (YSZ) with fs laser-induced micro-/nanostructures is demonstrated to exhibit unique anisotropic light-material interaction and nonlinear optical response on [100], [110], and [111] planes. Time-resolved reflectivity of YSZ after fs laser excitation is investigated by a pump-probe experiment, which is consistent with simulations through the plasma model combined with a two-temperature model. These results indicate two early ablation mechanisms: Coulomb explosion and melting. Anisotropic crack structures are formed due to thermal stress, which is always ignored in fs laser fabrication and is verified by Raman mapping and analysis of slip systems on different crystal planes. Through the z-scan measurement, the nonlinear absorption (NLA) of crack structures is effectively improved, and a nearly 18 times enhancement of the NLA coefficient is acquired in [100] samples, while a 2 times enhancement in [110] and [111] samples. Such great enhancement of NLA is mainly due to the abundant presence of crack structures and the increase of fs laser-induced oxygen vacancies in [100] YSZ. These results provide a potential way of utilizing fs laser to improve the nonlinearity for the technological development in nonlinear devices.