Search Results (68)

Degenerate third-order nonlinear optical (NLO) responses of organic molecules have a wide range of applications in science and engineering because they relate to the intensity-dependent refractive index (IDRI) and nonlinear absorption (NLA), such as two-photon absorption (TPA). Among the many molecular systems, open-shell molecular species such as intermediate singlet diradicaloids have attracted considerable attention because of their enhanced response, predicted theoretically by Nakano et al. Experimental studies for proofing and evaluating the enhanced nonlinearities play an important role in the development of the field. This tutorial review provides the solid fundamentals of the NLO processes of open-shell molecular species even to those who are not familiar with the experimental works. Its scope ranges from the basics of NLO responses, definitions, and interrelations of the key parameters of the responses, such as hyperpolarizability and TPA cross-section, to the experimental techniques used to evaluate them. Including the recent achievements, the evolution of experimental works on the TPA properties of singlet diradicaloids is also reviewed according to families of molecular structures. Full article

The optical and radiation shielding of PVA have been enhanced through embedding with ZnO/CuO/SWCNT (ZCS) nanocomposites. ZCS polymeric nanocomposites (PNCs) were prepared with the solution casting method. Scanning electron, optical microscopy and FT-IR procedures were performed to examine the surfaces’ morphology and structures’ modifications. UV–visible measurements were carried out to investigate the linear/nonlinear optical properties. The optical investigations show significant alterations in the optical parameters of PVA due to ZCS embedding. The UV–visible analysis shows that the optical parameters, including the transmittance, energy bandgap, refractive index, dielectric constants and optical conductivity of PVA, are tuned through ZCS embedding. The direct and indirect bandgap of PVA shrank from 5.42 eV and 4.99 eV (neat PVA) to 3.20 eV and 2.26 eV (10 wt.% ZCS PNCs). The nonlinear optical (NLO) constants (first order susceptibility (χ⁽¹⁾), third susceptibility (χ⁽³⁾) and refractive index (n₂)) of PVA were improved. Phy-X/PSD software was used to investigate the radiation shielding parameters of all samples. The linear attenuation coefficient (LAC), mean free path (MFP), half value layer (HVL), tenth value layer (TVL) and effective atomic number (Z_eff) of PVA were enhanced through ZCS embedding. It is found that the mass attenuation coefficient (MAC) of the neat PVA increased from 1.14 cm²/g to 7.96 cm²/g at 0.015 MeV. The HVL of PVA decreased from 30.2 cm to 20.6 cm, the TVL decreased from 100.3 cm to 68.5 cm and the MFP decreased from 43.6 cm to 29.8 cm upon embedding 10 wt.% of ZCS NCs at 15 MeV. The samples’ exposure buildup factor (EBF) and energy absorption buildup factor (EABF) in the photon energy range from 0.015 MeV to 15 MeV at 0.5 to 40 MFP values. This study proves that ZCS PNCs are advantageous for applications in optical and radiation shielding fields. Full article

Bismuth telluride (Bi₂Te₃) has attracted significant attention due to its broadband ultrafast optical response and strong nonlinearity at high laser fluence in the field of optoelectronic materials. The objective of this work is to study the effect of Al doping on the structure, linear optical properties, and nonlinear optical absorption behavior of Bi₂Te₃ thin films. The amorphous Al-doped Bi₂Te₃ thin films with varying Al doping concentrations were prepared using magnetron co-sputtering. The structure and linear optical properties were characterized using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, spectroscopic ellipsometry, and UV/Vis/NIR spectrophotometry. The third-order nonlinear optical absorption properties of Al: Bi₂Te₃ thin films were investigated using the open-aperture Z-scan system with a 100 fs laser pulse width at a wavelength of 800 nm and a repetition rate of 1 kHz. The results indicate that Al dopant reduces both the refractive index and extinction coefficient and induces a redshift in the optical bandgap. The optical properties of the films can be effectively modulated by varying the Al doping concentration. Compared with undoped Bi₂Te₃ thin films, Al-doped Bi₂Te₃ thin films exhibit larger nonlinear optical absorption coefficients and higher damage thresholds and maintaining high transmittance. These findings provide experimental evidence and a reliable approach for the further optimization and design of ultrafast nonlinear optical devices. Full article

The structure, bonding, and properties of diradicals, triradicals, and polyradicals have been investigated using broken symmetry (BS) molecular orbital (MO) and BS density functional theory (DFT) methods, which are regarded as the first steps in the mean-field approach toward strongly correlated electron systems (SCES). The natural orbital (NO) analyses of the BS MO and BS DFT solutions were performed to elucidate the natural orbitals of their occupation numbers, which are used for derivations of the diradical character (y) and several chemical indices for the open-shell molecules under investigation. These chemical indices are also obtained using SCES, the next theoretical step, which uses symmetry-recovered resonating BS (RBS) and multi-determinant methods such as multi-reference (MR) configuration interaction (CI) and MR-coupled cluster (CC) methods that employ the NOs generated in the first step. The nonlinear optical response properties of organic open-shell species were theoretically investigated with several procedures, such as MR CI (CC), the numerical Liouville, and Monte Carlo wavefunction methods, as the third step to SCES. The second-order hyperpolarizability (γ) of diradicals such as a phenalenyl radical dimer were mainly investigated in relation to the generation of quantum squeezed lights, which are used for the construction of the quantum entangled states for quantum optical devices such as quantum sensing and quantum computation. Basic quantum mechanical concepts, such as the Pegg–Barnett quantum phase operator, were also revisited in relation to the design and chemical synthesis of stable diradicals and polyradicals such as optical quantum molecular materials and future molecular qubits materials. Full article

The exploitation of high-performance third-order nonlinear optical (NLO) materials that have a favorable optical limit (OL) threshold is essential due to a rise in the application of ultra-intense lasers. In this study, a Cu-based MOF (denoted as Cu-bpy) was synthesized, and its third-order NLO and OL properties were investigated using the Z-scan technique with the nanosecond laser pulse excitation set at 532 nm. The Cu-bpy exhibits a typical rate of reverse saturable absorption (RSA) with a third-order nonlinear absorption coefficient of 100 cm GW⁻¹ and a favorable OL threshold of 0.75 J cm⁻² (at a concentration of 1.6 mg mL⁻¹), which is lower than that of most NLO materials that have been reported on so far. In addition, a DFT calculation was performed and was in agreement with our experimental results. Furthermore, the mechanism of the third-order NLO properties was illustrated as one-photon absorption (1PA). These results investigate the relationship between the structure and the nonlinear optical properties of Cu-bpy, and provide an experimental and theoretical basis for its use in optical limiting applications. Full article

In recent years, the fabrication of materials with large nonlinear optical coefficients and the investigation of methods to enhance nonlinear optical performance have been in the spotlight. Herein, the bismuth telluride (Bi₂Te₃) thin films were prepared by radio-frequency magnetron sputtering and annealed in vacuum at various temperatures. The structural and optical properties were characterized and analyzed using X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, spectroscopic ellipsometry, and UV/VIS/NIR spectrophotometry. The third-order optical nonlinearities of Bi₂Te₃ thin films were investigated using the Z-scan technique, employing a 100 fs pulse width at an 800 nm wavelength. It is found that the crystallinity and the average grain size of the films increase with the annealing temperature. Meanwhile, the extinction coefficient of the annealed films increased, accompanied by a redshift in the optical bandgap. All samples exhibit pronounced saturable absorption and self-focusing behaviors. The nonlinear absorption coefficient and nonlinear refractive index of Bi₂Te₃ films annealed at 300 °C were found to be 2.44 times and 1.85 times higher than those of the as-deposited films, respectively. These findings demonstrate that annealing treatment is an effective approach to tuning the crystalline structure and linear optical properties of Bi₂Te₃ films while simultaneously enhancing their nonlinear optical performance. Full article

In this report, the nonlinear optical (NLO) properties of titanium dioxide nanoparticles (TiO₂ NPs) have been explored experimentally using femtosecond laser light along with the Z-scan approach. The synthesis of TiO₂ NPs was carried out in distilled water through nanosecond second harmonic Nd:YAG laser ablation. Characterization of the TiO₂ NPs colloids was conducted using UV-visible absorption spectroscopy, transmission electron microscopy (TEM), inductively coupled plasma (ICP), and energy-dispersive X-ray spectroscopy (EDX). The TEM analysis indicated that the size distribution and average particle size of the TiO₂ NPs varied from 8.3 nm to 19.1 nm, depending on the laser ablation duration. The third-order NLO properties of the synthesized TiO₂ NPs were examined at different excitation laser wavelengths and incident powers through both open- and closed-aperture Z-scan techniques, utilizing a laser pulse duration of 100 fs and a high repetition rate of 80 MHz. The nonlinear absorption (NLA) coefficient and nonlinear refractive (NLR) index of the TiO₂ NPs colloidal solutions were found to be influenced by the incident power, excitation wavelength, average size, and concentration of TiO₂ NPs. Maximum values of 4.93 × 10⁻⁹ cm/W for the NLA coefficient and 15.39 × 10⁻¹⁵ cm²/W for the NLR index were observed at an excitation wavelength of 800 nm, an incident power of 0.6 W, and an ablation time of 15 min. The optical limiting (OL) effects of the TiO₂ NPs solution at different ablation times were investigated and revealed to be concentration and average size dependent. An increase in concentration results in a more limiting effect. Full article

This study investigates the optical properties of diffraction gratings using localized surface plasmon resonance (LSPR) with metal nano-hemispheres. We fabricated metal nano-hemisphere gratings (MNHGS) with Ga, Ag, and Au and examined their wavelength-selective diffraction properties. Our findings show that these gratings exhibit peak diffraction efficiencies at 300 nm, 500 nm, and 570 nm, respectively, corresponding to the LSPR wavelengths of each metal. The MNHGs were created through thermal nanoimprint and metal deposition, followed by annealing. The experimental and simulation results confirmed that the MNHGs selectively diffract light at their resonance wavelengths. Applying these findings to third-order nonlinear laser spectroscopy (MPT-TG method) enhances measurement sensitivity by reducing background noise through the selective diffraction of pump light while transmitting probe light. This innovation promises a highly sensitive method for observing subtle optical phenomena, enhancing the capabilities of nonlinear laser spectroscopy. Full article

Spherical quantum wells (SQWs) have proven to be excellent materials for suppressing Auger recombination due to their expanded confinement volume. However, research on the factors and mechanisms of their high-intensity optical properties, such as multiexciton properties and third-order optical nonlinearities, remains incomplete, limiting further optimization of these properties. Here, a series of CdS/CdSe (xML)/CdS SQWs with varying CdSe layer thicknesses were prepared. The modulation effects of CdSe shell variations on the PL properties, defect distribution, biexciton binding energy, and third-order optical nonlinearities of the SQWs were investigated, and their impact on the material’s multiexciton properties was further analyzed. Results showed that the typical CdS/CdSe(3ML)/CdS sample exhibited a large volume-normalized two-photon absorption cross-section (18.17 × 10² GM/nm³) and favorable biexciton characteristics. Optical amplification was observed at 12.4 μJ/cm² and 1.02 mJ/cm² under one-photon (400 nm) and two-photon (800 nm) excitation, respectively. Furthermore, different amplified spontaneous emission spectra were observed for the first time under one/two-photon excitation. This phenomenon was attributed to thermal effects overcoming the biexciton binding energy. This study provides valuable insights for further optimizing multiexciton gain characteristics in SQWs and developing optical gain applications. Full article

A glass composition using TeO₂-K₂TeO₃-Nb₂O₅-BaF₂ co-doped with Er₂O₃/Ho₂O₃ and Er₂O₃/Yb₂O₃ was successfully fabricated. Its thermal stability and physical parameters were studied, and luminescence spectroscopy of the fabricated glasses was conducted. The optical band gap, E_opt, decreased from 2.689 to 2.663 eV following the substitution of Ho₂O₃ with Yb₂O₃. The values of the refractive index, third-order nonlinear optical susceptibility (χ⁽³⁾), and nonlinear refractive index (n₂) of the fabricated glasses were estimated. Furthermore, the Judd–Ofelt intensity parameters ${\Omega }_t (t=2,4,6)$, radiative properties such as transition probabilities (A_ed), magnetic dipole-type transition probabilities (A_md), branching ratios (β), and radiative lifetime (τ) of the fabricated glasses were evaluated. The emission cross-section and FWHM of the ⁴I_13/2→⁴I_15/2 transition around 1.54 μm of the glass were reported, and the emission intensity of the visible signal was studied under 980 nm laser excitation. The material might be a useful candidate for solid lasers and nonlinear amplifier devices, especially in the communications bands. Full article

Silicon carbide (SiC) electronics has seen a rapid development in industry over the last two decades due to its capabilities in handling high powers and high temperatures while offering a high saturated carrier mobility for power electronics applications. With the increased capacity in producing large-size, single-crystalline SiC wafers, it has recently been attracting attention from academia and industry to exploit SiC for integrated photonics owing to its large bandgap energy, wide transparent window, and moderate second-order optical nonlinearity, which is absent in other centrosymmetric silicon-based material platforms. SiC with various polytypes exhibiting second- and third-order optical nonlinearities are promising for implementing nonlinear and quantum light sources in photonic integrated circuits. By optimizing the fabrication processes of the silicon carbide-on-insulator platforms, researchers have exploited the resulting high-quality-factor microring resonators for various nonlinear frequency conversions and spontaneous parametric down-conversion in photonic integrated circuits. In this paper, we review the fundamentals and applications of SiC-based microring resonators, including the material and optical properties, the device design for nonlinear and quantum light sources, the device fabrication processes, and nascent applications in integrated nonlinear and quantum photonics. Full article

Simultaneous interrogation of pump and probe beams interacting in ZnO nanostructures of a two-wave mixing is proposed for dual-path data processing of optical signals by nonlinear optical effects. An enhancement in third-order nonlinear optical properties was exhibited by Al-doped ZnO thin films. Multiphoton absorption and nonlinear refraction were explored by the z-scan technique at 532 nm with nanosecond pulses. The evolution of the optical Kerr effect in the ZnO thin films was analyzed as a function of the incorporation of Al in the sample by a vectorial two-wave mixing method. Electrical and photoconductive effects were evaluated to further characterize the influence of Al in the ZnO solid samples. Potential applications of nonlinear optical parameters for encoding and encrypting information in light can be envisioned. Full article

This review describes the two-photon absorption properties of dendrimers, which are arborescent three-dimensional macromolecules differing from polymers by their perfectly defined structure. The two-photon absorption process is a third order non-linear optical property that is attractive because it can be used in a wide range of applications. In this review, dendrimers that were studied for their two-photon absorption properties are first described. Then, the use of dendritic TPA chromophores for light harvesting, photopolymerization, optical power limitation, cell imaging, singlet oxygen generation, and photodynamic therapy is described. This review thus proposes an overview of the properties and possible applications of two-photon absorbing dendrimers. Full article

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 $n_2=3.1\times {10}^{-15}{\mathrm{c}\mathrm{m}}^2/\mathrm{W}$. Full article

The tuning of second (SHG) and third (THG) harmonic emission is studied in the model system LiNb${ }_{1-x}$Ta${ }_x$O${ }_3$ ($0\le x\le 1$, LNT) between the established edge compositions lithium niobate (LiNbO${ }_3$, $x=0$, LN) and lithium tantalate (LiTaO${ }_3$, $x=1$, LT). Thus, the existence of optical nonlinearities of the second and third order is demonstrated in the ferroelectric solid solution system, and the question about the suitability of LNT in the field of nonlinear and quantum optics, in particular as a promising nonlinear optical material for frequency conversion with tunable composition, is addressed. For this purpose, harmonic generation is studied in nanosized crystallites of mechanochemically synthesized LNT using nonlinear diffuse reflectometry with wavelength-tunable fundamental femtosecond laser pulses from 1200 nm to 2000 nm. As a result, a gap-free harmonic emission is validated that accords with the theoretically expected energy relations, dependencies on intensity and wavelength, as well as spectral bandwidths for harmonic generation. The SHG/THG harmonic ratio ≫1 is characteristic of the ferroelectric bulk nature of the LNT nanocrystallites. We can conclude that LNT is particularly attractive for applications in nonlinear optics that benefit from the possibility of the composition-dependent control of mechanical, electrical, and/or optical properties. Full article