Bulk crystal growth,spectral, optical,thermal, electrical and third-order NLO properties of benzylidene malononitrile derivative single crystal: a promising material for nonlinear optical device applications

Bulk organic intramolecular charge transfer nonlinear optical single crystal of 2-(2,4-dimethoxybenzylidene) malononitrile (DMM) with the sizes of 24?×?18?×?13 mm³ have been successfully grown by slow evaporation solution growth technique at 35 °C using acetone as the solvent. The lattice parameters of the grown DMM crystal was evaluated by single crystal X-ray diffraction analysis. The optical transmittance (T) data was taken from the well-polished crystal of DMM, and cut-off wavelength (λ?=?483 nm) was identified by UV–Vis spectral studies. Thermal stability and melting point (145.78 °C) were studied with TGA–DSC analysis. The low value of the dielectric constant (ε_r) of DMM suggests that the crystal can be used in the microelectronics industry. The laser-induced damage threshold experiment shows that the grown DMM bulk crystal possess an excellent resistance to laser radiation with a high threshold up to 1.75 GW/cm², much larger than those of several known organic and inorganic NLO materials. The DMM crystal exhibits positive optical non-linearity and reverse saturation absorption. It also exhibited a nonlinear refractive index (n₂) in the order of 10^?11 m²/W, a nonlinear absorption coefficient (β) in the order of 10^?5 m/W, third order non-linear susceptibility (χ⁽³⁾) in the order of 10^?5 esu and a second-order molecular hyperpolarizability (γ) in the order of 10^?33 esu. All the above results indicate that DMM has a potential application as a useful NLO candidate.     

Dispersion of the linear and nonlinear optical susceptibilities of disilver germanium sulfide from DFT calculations

The dispersion of the linear and nonlinear optical susceptibilities is calculated for disilver germanium sulfide (Ag₂GeS₃) using the all-electron full potential linearized augmented plane wave (FP-LAPW) method. Calculations are performed with four exchange correlations namely local density approximation (LDA), general gradient approximation (GGA), Engel–Vosko generalized gradient approximation (EVGGA), and modified Becke–Johnson potential (mBJ). Our calculations give a band gap of 0.40 eV (LDA), 0.42 eV (GGA), 1.03 eV (EVGGA), and 1.30 eV (mBJ) in comparison with our measured gap (1.98 eV). The mBJ exchange correlation gives the best agreement with experiment. We find that the calculated linear optical susceptibilities of Ag₂GeS₃ show considerable anisotropy which is useful for second harmonic generation and optical parametric oscillation. To analyze the spectra of the calculated χ ₁₁₃ ⁽²⁾ (ω), χ ₂₃₂ ⁽²⁾ (ω), χ ₃₁₁ ⁽²⁾ (ω), χ ₃₂₂ ⁽²⁾ (ω), and χ ₃₃₃ ⁽²⁾ (ω), we have correlated the features of these spectra with the features of ?₂(ω) spectra as a function of ω/2 and ω. From the calculated dominant component |χ ₃₃₃ ⁽²⁾ (ω)|, we find that the microscopic second-order hyperpolarizability, β₃₃₃, the vector components along the dipole moment direction is 41.2 × 10^?30 esu at static limit and 222.9 × 10^?30 esu at λ = 1064 nm.     

Nonlinear optics in materials: integral transformation of optical four-wave mixing spectra

We analyze the estimation of the third-order susceptibility χ⁽³⁾ of nonlinear optical (NLO) materials by means of a Hilbert transformation applied to their optical four-wave mixing spectra. In particular, the coherent anti-Stokes Raman scattering (CARS) spectrum is considered. In this case, the integral line-shape processing enables the determination of the excitation profile for resonance CARS (RCARS), or the ratio χ_R/χ_EL between the Raman susceptibility and the electronic susceptibility, if nonresonance CARS is performed. As an illustration, we use this procedure to evaluate χ_EL for a NLO polymer in solution.     

Donor/acceptor effects on the nonlinear optical properties of 1,3 diphenyl propenones

Employing the single beam Z-scan technique with nanosecond laser pulses at 532 nm, the refractive and absorptive nonlinearities of donor and acceptor substituted (2E)-1-(3,4-dimethoxyphenyl)-3-phenylprop-2-en-1-one have been studied. The sign of the nonlinear index of refraction (n ₂) is found to be negative and the magnitude of n ₂ is in the order of 10^?11 esu. The second-order molecular hyperpolarizability (γ_h) is calculated to be in the order of 10^?32 esu. The variation of nonlinear absorption coefficient (β_eff) with input intensity (I ₀) is studied and the nonlinear absorption mechanism is found to be reverse saturable absorption (RSA). The enhancement of nonlinearity due to the donor and acceptor substitution is in accordance with the variation in π electron delocalization in the molecules. The compounds exhibit good optical limiting as well.     

Dispersion of the Nonlinear Optical Susceptibility in Single‐Wall Carbon Nanotubes

Abstract

We have calculated the dispersive behavior of the third‐order nonlinear susceptibility χ⁽³⁾ (?ω₃; ω₁, ω₁, ?ω₂) in single‐wall carbon nanotubes (SWCNTs) responsible for optical frequency mixing of the form ω₃ = 2ω₁ ? ω₂. The dispersive resonance of χ⁽³⁾ (?ω₃; ω₁, ω₁, ?ω₂) is shown to occur when the frequency ω₃ = 2ω₁ ? ω₂ is generated near the band gap of SWCNTs due to three‐wave mixing. A very sharp peak of χ⁽³⁾ (?ω₃; ω₁, ω₁, ?ω₂) reaching extremely high values ～10^?4 esu at the newly generated frequency ω₃ can be observed when not only ω₃ is close to the band gap of the system, but also when the frequencies of incident fields are near such a resonance.     

Picosecond nonlinear optical studies of gold nanoparticles synthesised using coriander leaves (Coriandrum sativum)

The results are presented from the experimental picosecond nonlinear optical (NLO) studies of gold nanoparticles synthesised using coriander leaf (Coriandrum sativum) extract. Nanoparticles with an average size of ～30?nm (distribution of 5–70?nm) were synthesised according to the procedure reported by Narayanan et al. [Mater. Lett. 2008, 62, 4588–4591]. NLO studies were carried out using the Z-scan technique using 2?ps pulses near 800?nm. Open-aperture data suggested saturation absorption as the nonlinear absorption mechanism, whereas closed-aperture data suggested a positive nonlinearity. The magnitude of third-order nonlinearity was estimated to be (3.3?±?0.6)?×?10^?13?esu. A solvent contribution to the nonlinearity was also identified and estimated. A comparison is attempted with some recently reported NLO studies of similar gold nanostructures.     

Synthesis,z-scan and degenerate four wave mixing characterization of certain functionalized photosensitive polyesters containing ortho-hydroxyazo chromophores

The preparation and NLO characterization of photosensitive polyesters containing azoaromatic residues in the molecular backbone, functionalized with orthohydroxy chromophores is presented. Samples were studied for its UV–vis absorption, FT-IR and intensity dependent nonlinear absorption properties. Nonlinear characterization was carried out with z-scan using frequency doubled, Q-switched Nd:YAG laser operating at 532 nm. The closed aperture z-scan spectra reveal the self defocusing effects of the samples with negative nonlinearity coefficient (n₂) showing values as high as −1.28 × 10⁻¹⁰ (esu) for certain samples and the corresponding third order susceptibility coefficient of the order of 29.9 × 10⁻¹² (esu). Degenerate four wave mixing technique was employed to substantiate the findings. The numerical fits show that the molecules exhibit reverse saturable absorption. A study of beam fluence dependence of nonlinear absorption coefficient (β_eff) has been presented. All phenomena indicate that molecules are reverse saturable absorbers whose optical limiting property gets enhanced with increasing conjugation length.     

Optical bistability for ZnO–Nb2O5–TeO2 glasses

We examined the optical nonlinear properties of ZnO–Nb₂O₅–TeO₂. The absorption and Raman spectra were measured, the third-order nonlinear susceptibility was determined by degenerated four wave mixing technique. The magnitude of χ⁽³⁾ is about 1.0 × 10⁻¹² esu, larger than that of silica glasses, and the optical bistability was observed in a Fabry–Perot cavity.     

Structural,optical, electrical properties of new hybrid organic–inorganic NLO single crystal: bis(1H-benzotriazole) hexaaqua-zinc bis(sulfate) tetrahydrate (BZS)

A new hybrid organic–inorganic nonlinear (NLO) single crystal, Bis(1H-benzotriazole) hexaaqua-zinc bis(sulfate) tetrahydrate (BZS), has been successfully synthesized and the single crystals were grown by slow evaporation solution growth technique (SESG) using Millipore water as a solvent. The structure of the BZS crystal was solved and refined by single-crystal X-ray diffraction and demonstrates that the grown crystals belong to a triclinic system with the space group P-1. The asymmetric part of the titled compound contains isolated organic cation (C₆H₆N₃)₂, metallic cation [Zn(H₂O)₆]²⁺, sulfate anion (SO₄)^2? and free H₂O molecules. The interplay between the wide number of intermolecular interaction such as O–H···O, N–H···O, C–H···O and π–π stacking interactions were discussed. The optical transmittance spectrum shows that the crystal is excellent transmittance in the entire Vis–NIR region with the cutoff wavelength at 345 nm. The presences of expected functional groups were identified by Fourier transform infrared spectroscopy. The dielectric measurements were carried out at different temperature in the frequency range 100 Hz–5MHz. Furthermore, the studies of its third-order NLO properties using a Z-scan technique demonstrate that the BZS crystal possesses a strong reverse saturable absorption (RSA) and the self-focusing (SF) nature with large second order hyperpolarizability (γ?=?6.24?×?10^?34 esu). All the results indicate that BZS crystal might be the potential candidate for the third-order NLO applications.     

Large third-order optical nonlinearity of SrBi2Nb2O9 thin films fabricated by pulsed laser deposition

SrBi₂Nb₂O₉ (SBN) thin films with a single phase of layered perovskite structure have been fabricated on fused quartz substrates at room temperature by pulsed laser deposition. The XRD and AFM analysis indicated that the films had better crystallinity, less rough surface morphology, and larger grain size with increasing oxygen pressure. The nonlinear optical properties of the samples were determined using a single beam Z-scan technique at a laser wavelength of 532 nm with laser duration of 25 ps. The real and imaginary parts of the third-order nonlinear optical susceptibility χ⁽³⁾ of the films were measured to be 3.18 × 10^− 8 esu and 5.94 × 10^− 9 esu, respectively.     

χ measurements and optical limiting studies of 2-chloro-5-nitro-N′-[(1E)-phenylmethylidene] benzohydrazide with substituents

The nonlinear optical properties of hydrazones substituted with different donor groups were studied using single beam Z-scan technique with nanosecond laser pulses at 532 nm. The nonlinear response in these molecules was found to increase with increase in the donor strength of the substituted group. The χ⁽³⁾ value of these molecules is found to be of the order of 10⁻¹³ esu. The nonlinear refractive index (n₂) of the samples is found to be negative and the largest value of n₂ obtained for the strong donor-substituted molecule is −8.83 × 10⁻¹¹ esu. All samples show good optical limiting behavior at 532 nm. The best optical limiting behavior was observed with the molecule substituted by a strong electron donor.     

Optical properties of binary composite materials with two nonlinear components

Abstract

A new formulation is presented for the calculation of effective dielectric magnitudes of two-component composites in which both components (the host matrix particles and the embedded particles) exhibit nonlinear behaviour of the Kerr type. It is predicted that, under certain conditions, two nonlinear component composites can exhibit optical bistable behaviour as a function of the shape and concentration of the embedded particles, the dielectric contants of the components, the intensity of the external electric field (power density) and the intrinsic third-order nonlinear optical susceptibilities χ⁽³⁾ _p and χ⁽³⁾ _m of the nonlinear components. It is also deduced that, as the power density increases, the effective third-order nonlinear optical susceptibility χ⁽³⁾ of the composite exhibits a clear transition from values close to χ⁽³⁾ _p (low power density) to χ⁽³⁾ _m (high power density). Therefore, it is shown that the optical response of binary composites dramatically changes at moderate and high power densities. A comparison is performed between the optical response of a real two nonlinear component composite and that of a composite with a single nonlinear component.     

Nonlinear optical behavior of alkyne terminated phthalocyanines in solution and when embedded in polysulfone as thin films: Effects of aggregation

We report here for the first time, on the comparative studies of the photophysical and optical limiting behavior of our two novel phthalocyanines namely 2(3), 9(10), 16(17), 23(24)-tetrakis-(4-(5-methylhex-1-yn-3-yloxy)) phthalocyanines 2, and 2(3), 9(10), 16(17), 23(24)-tetrakis-(4-(5-methylhex-1-yn-3-yloxy)) phthalocyaninato zinc (II) (3) in solution and thin films. Nonlinear optical (NLO) properties of the samples in solution and contained in polysulfone (PSU) thin films were evaluated using Z-scan technique at 532 nm and 10 ns pulsed duration. Effects of aggregation and disaggregation on the NLO performance of metal-free phthalocyanine are reported in detail. Our findings showed that the prepared Pcs show larger nonlinear absorption coefficient and lower limiting thresholds when embedded in polysulfone films compared to in solutions. The values of nonlinear susceptibility and hyperpolarizability recorded for 3-PSU in this work are respectively, ∼2.09 × 10⁻⁸ esu and ∼1.02 × 10⁻²⁶ esu. These values are among the largest values reported for phthalocyanines and other macrocycles doped on polymer matrices.     

Nonlinear optical investigations on Al doping ratio in ZnO thin film under pulsed Nd:YAG laser irradiation

In the present study, it has been reported on the effect of Al doping on linear and nonlinear optical properties of ZnO thin films synthesized by spray pyrolysis method. The structural properties of ZnO thin films with different Al doping levels (0–4 wt%) were analyzed using X-ray diffraction (XRD). The results obtained from XRD analysis indicated that the grain size decreased as the Al doping value increased. The UV–Vis diffused refraction spectroscopy was used for calculation of band gap. The optical band gap of Al-doped ZnO (AZO) thin films is increased from 3.26 to 3.31 eV with increasing the Al content from 0 to 4 wt%. The measurements of nonlinear optical properties of AZO thin films have been performed using a nanosecond Nd:YAG pulse laser at 532 nm by the Z-scan technique. The undoped ZnO thin film exhibits reverse saturation absorption (RSA) whereas the AZO thin films exhibit saturation absorption (SA) that shows RSA to SA process with adding Al to ZnO structure under laser irradiation. On the other hand, all the films showed a self-defocusing phenomenon because the photons of laser stay on below the absorption edge of the ZnO and AZO films. The third-order nonlinear optical susceptibility, χ⁽³⁾, of AZO thin films, was varied from of the order of 10^?5–10^?4 esu. The results suggest that AZO thin films may be promising candidates for nonlinear optical applications.     

IR-stimulated second harmonic generation in Sb2Te2 Se-BaF2-PbCl2 glasses

Abstract

Theoretically predicted and experimentally observed infraredinduced second-harmonic generation of glasses in the mid-infrared spectral region can be described by fifth-order nonlinear optical susceptibility. The effect is observed in the mid-IR region when the value of the electronic energy gap is comparable to the energies of actual phonons participating in the anharmonic (non-centrosymmetric) electron-phonon interactions. As subjects for investigation, chalcohalide Sb₂Te₂Se-BaF₂-PbCl₂ glasses were chosen. They are transparent, over a spectral range of 1.1–10.9 μm. The second-harmonic generation (SHG) output signal within the 1.5–4.8 μm spectral range has significant spectral dependence. Correlation of the SHG spectral maxima positions with spectral positions of anharmonic phonon frequencies confirms that the fifth-order steady-state process occurs due to cascading processes and IR-induced charge density non-centrosymmetry. A maximum value of the SHG is achieved at a pump-probe delay time of 18–36 ps, which is typical for anharmonic electron-phonon interactions. As temperature rises, the values of the photoinduced SHG signal susceptibility increases up to 3 × 10^?39 m⁴/V⁴. The SHG signal reaches a saturation point for the IR-pump power densities of about 0.8 GW/cm², which corresponds to the output SHG intensities of about 6 × 10^?4 with respect to fundamental one. The values of the diagonal fifth-order tensor component χ^(2ω) _xxxxx are at least one order of magnitude larger than the off-diagonal tensor components.     

Growth, linear and nonlinear optical and, laser damage threshold studies of organometallic crystal of MnHg(SCN)4

Single crystals of bimetallic MnHg(SCN)₄ (abbreviated as MMTC) are grown by slow cooling method and the second and third order optical nonlinearities are investigated by Kurtz and Perry powder SHG test and single beam Z-scan technique respectively. The influences of SCN ligand in modifying the NLO properties are discussed and the results are compared with other organometallic crystals. The nonlinear refractive index, absorption coefficient and third order susceptibility are estimated to be −1.88 × 10⁻¹¹ cm²/W, 8.65 × 10⁻⁶ cm/W and 6.58 × 10⁻⁹ esu, respectively. The optical absorption of MMTC single crystal was recorded and the corresponding direct band gap is found to be 4.2 eV. The phase matching and laser induced damage threshold studies are also carried out. The FT-IR and photoluminescence spectroscopic techniques were employed to identify the composition and luminescence nature of the crystal.     

Surface plasmon-enhanced third-order optical non-linearity of silver triangular nanoplate

Abstract

We have obtained Ag triangular nanoplates with plasmon resonance bands locating from 750 to 950 nm by wet chemical method. The third-order optical non-linear response property of Ag triangular nanoplate is investigated using z-scan technique. The incident wavelength dependence of χ⁽³⁾ (the third-order susceptibility) shows the third-order nonlinear behaviour of Ag nanoplate is greatly modified by its plasmon resonance property, for the largest value of χ⁽³⁾ is observed around the wavelength of plasmon resonant peak. Also, we find the maximum value of Ag nanoplate’s χ⁽³⁾ is 7.46 × 10^?11 esu, which is about 1–3 orders of magnitude larger than that of many other nanomaterials including Au nanorod, nanobipyramid and nanocube, as well as Ag nanosphere and nanodisc. This fact indicates the Ag triangular nanoplate is a kind of useful nonlinear material with larger third-order nonlinearity, showing great potentials in the explorations of functional non-linear devices.     

Third order nonlinear optical susceptibility of fluorescein-containing polymers determined by electro-absorption spectroscopy

Novel polymers containing xanthene groups with high dye concentrations were prepared, and their third order nonlinear optical properties were studied by electroabsorption spectroscopy technique. The polymers were amorphous with refractive indices above 1.6 in the non-resonant region. The UV-Visible absorption spectra indicate the fluoresceins molecules in the polymers are H-aggregated. They showed third order nonlinear susceptibility, χ⁽³⁾ (−ω:ω, 0, 0), of 2.5-3.5 × 10⁻¹² esu.     

Nonlinear optical characterization and measurement of optical limiting threshold of CdSe quantum dots prepared by a microemulsion technique

CdSe quantum dots prepared by micro emulsion technique shows quantum confinement effect and broad emission at 532 nm. These quantum dots have about 4.35 nm size, and they exhibit good nonlinear effects which are measured using z-scan technique. The samples have a reverse saturation in the nonlinear absorption as nonlinear optical absorption coefficient β is 2.545 × 10⁻¹⁰ W m⁻¹ and nonlinear optical refraction coefficient n ₂ is −1.77 × 10⁻¹⁰ esu. The third-order nonlinear optical susceptibility is found to be 4.646 × 10⁻¹¹ esu and also the figure of merit is 2.01 × 10⁻¹² esu m. The optical limiting threshold which is found to be 0.346 GW/cm² makes it a good candidate for device fabrication.     

Quantitative Polarization-Resolved Second-Harmonic-Generation Microscopy of Glycine Microneedles

Second-harmonic generation (SHG) is a nonlinear optical process that can provide disease diagnosis through characterization of biological building blocks such as amino acids, peptides, and proteins. The second-order nonlinear susceptibility tensor χ⁽²⁾ of a material characterizes its tendency to cause SHG. Here, a method for finding the χ⁽²⁾ elements from polarization-resolved SHG microscopy in transmission mode is presented. The quantitative framework and analytical approach that corrects for micrometer-scale morphology and birefringence enable the determination and comparison of the SHG susceptibility tensors of β- and γ-phase glycine microneedles. The maximum nonlinear susceptibility coefficients are d₃₃ = 15 pm V⁻¹ for the β and d₃₃ = 5.9 pm V⁻¹ for the γ phase. The results demonstrate glycine as a useful biocompatible nonlinear material. This combination of the analytical model and polarization-resolved SHG transmission microscopy is broadly applicable for quantitative SHG material characterization and diagnostic imaging.