Synthesis and investigation of nonlinear optical properties of semiconductor ZnS nanoparticles

ZnS nanoparticles were prepared by a simple chemical method and using PVP (poly vinylpyrrolidone) as capping agent. The sample was characterized by UV-vis spectrophotometer, X-ray diffraction (XRD) and Z-scan technique. XRD pattern showed that the ZnS nanoparticles had zinc blende structure with an average size of about 2.18 nm. The value of band gap of these nanoparticles was measured to be 4.20 eV. The nonlinear optical properties of ZnS nanoparticles in aqueous solution were studied by Z-scan technique using CW He-Ne laser at 632.8 nm. The nonlinear absorption coefficient (β) was estimated to be as high as 3.2×10⁻³ cm/W and the nonlinear refractive index (n₂) was in order of 10⁻⁸ cm²/W. The sign of the nonlinear refractive index obtained negative that indicated this material exhibits self-defocusing optical nonlinearity.     

Single beam Z-scan measurement of the third order optical nonlinearities of styryl7 dye

The optical nonlinearity of styryl7 dye in ethanol solution at different concentrations has been studied using pulsed Nd:YAG laser at 532 nm as the source of excitation. The optical responses were characterized by measuring the intensity dependent refractive index (n₂) of the medium using the Z-scan technique. The open aperture Z-scan trace of the dye in solution displayed saturable absorption. The closed aperture Z-scan trace of the dye exhibited a negative nonlinearity. The styryl7 dye at 1 mM concentration exhibited nonlinear refractive co-efficient n₂ = −1.24 × 10⁻⁸ cm²/W, nonlinear absorption coefficient β = − 3.9 × 10⁻⁴ cm/W and real and imaginary parts of third-order nonlinear optical susceptibility χ³ = 3.26 × 10⁻⁶ esu in ethanol. These results showed that the dye has potential application in nonlinear optics.     

Study of optical nonlinearity of functionalized multi-wall carbon nanotubes by using degenerate four wave mixing and Z-scan techniques

The phase conjugation geometry of degenerate four wave mixing (DFWM) technique has been employed to study the third-order optical nonlinear susceptibility (χ³) and second-order hyperpolarizability of multi-wall carbon nanotubes (MWCNTs). MWCNTs were grown by thermal chemical vapor deposition method and, subsequently functionalized with carboxylic acid group to improve their solubility in an organic solvent, ethylene glycol. The average hyperpolarizability for each carbon atom has been found to be 4.74 × 10⁻⁴⁶ m⁵/V² for the pump pulse of 8 ns at 532 nm. Decreasing the pulse width of the pump laser decreases the average value of hyperpolarizability. The absorption spectra show a monotonous increase from IR through visible and give an opportunity to estimate the imaginary part of the χ³ by the open aperture Z-scan technique.     

Anisotropic nonlinear optical absorption of gold nanorods in a silica matrix

Nanocomposite films consisting of gold nanospheres or gold nanorods embedded in a silica matrix have been prepared using a hybrid deposition technique consisting of plasma-enhanced chemical vapor deposition of SiO₂ and co-sputtering of gold, followed by annealing at 900 °C. Subsequent irradiation with 30 MeV heavy ions (Cu⁵⁺) was used to form gold nanorods. Linear and nonlinear optical properties of this material are closely related with the surface plasmon resonance in the visible. The nonlinear absorption coefficient (α₂@532 nm) for the films containing gold nanospheres was measured by Z-scan and P-scan techniques, and it was found to be isotropic and equal to −4.8 × 10⁻² cm/W. On the contrary, gold nanorods films exhibited two distinct surface plasmon resonance absorption bands giving rise to a strong anisotropic behavior, namely a polarization-dependent linear absorption and saturable absorption. Z-scan and P-scan measurements using various light polarization directions yielded nonlinear absorption coefficient (α₂@532 nm) values varying from −0.9 × 10⁻² cm/W up to −3.0 × 10⁻² cm/W. Linearity of the P-scan method in the context of nanocomposite saturable absorption is also discussed.     

Z-scan measurement for the nonlinear absorption and the nonlinear refraction of poly1,4-diazophenylene-bridged-tris(8-hydroxy-quinoline) aluminum (PDPAlq3)

The nonlinear optical properties of the poly1,4-diazophenylene-bridged-tris(8-hydroxy-quinoline) aluminum (PDPAlq₃) solution were studied using single beam Z-scan technique with a continuous-wave Diode laser radiation at 657.2 nm with 10 Hz repetition rate. The results show that the solution of PDPAlq₃ exhibits large nonlinear refractive index (n₂ = −1.7642 × 10⁻¹² m²/W) and nonlinear absorption coefficient (β = 1.12 × 10⁻⁶ m/W). The negative sign of the nonlinear refractive index n₂ indicates that the material exhibits self-defocusing optical nonlinearity. The evaluation of the figure of merit (W = 1.8) shows that the solution of PDPAlq₃ is sufficient for application in all-optical switching technology. These results show that the solution of PDPAlq₃ have potential application in nonlinear optics.     

Nonlinear optical properties of Cu nanoclusters by ion implantation in silicate glass

Metal nanocluster composite glass prepared by 180 keV Cu ions into silica with dose of 1 × 10¹⁷ ions/cm² has been studied. The microstructural properties of the nanoclusters were analysed by optical absorption spectra and transmission electron microscopy (TEM). Third-order nonlinear optical properties of the nanoclusters were measured at 1064 nm and 532 nm excitations using Z-scan technique. The nonlinear refraction index, nonlinear absorption coefficient, and the real and imaginary parts of the third-order nonlinear susceptibility were deduced. The mechanisms responsible for the nonlinear response were discussed. Absolute third-order nonlinear susceptibility χ⁽³⁾ of this kind of sample was determined to be 2.1 × 10⁻⁷ esu at 532 nm and 1.2 × 10⁻⁷ esu at 1064 nm, respectively.     

The nonlinear refraction and nonlinear absorption in 4-(4,6-diaminopyrimidin-2-ylthio) substituted double-decker Lu(III) phthalocyanine

A 4-(4,6-diaminopyrimidin-2-ylthio) substituted double-decker Lu(III) phthalocyanines (4) have been prepared and characterized by elemental analysis, IR, UV-vis and ¹H NMR spectroscopies. The nonlinear refractive index, nonlinear absorption and the optical limiting (OL) performance of the compound 4 in a 0.5 mm spectroscopic cell in DMF solution were investigated by using 4 ns pulse laser at 532 nm. Z-scan experiments have been conducted between 0.24 and 2.39 GW/cm² peak intensities for 10 Hz repetition rate and also between 2.39 and 23.89 GW/cm² peak intensities for 1 Hz repetition rate. The thermal effect contributes to the nonlinear response of the material higher than 0.72 GW/cm² peak intensity at 10 Hz. We measured the effective nonlinear refractive index of the material as 1.2×10⁻¹¹ esu at 3.5×10⁻⁴ M concentration with the peak intensity less than 0.72 GW/cm² and we found that nonlinear absorption was very small. On the other hand, when concentration is increased to 2.4×10⁻³ M material's nonlinear absorption becomes dominant mechanism for the nonlinear response and the compound 4 indicates OL behavior at 2.4×10⁻³ M concentration.     

Synthesis and third-order optical nonlinearities of nickel complexes of 8-hydroxyquinoline derivatives

A nickel complex of 5-(acrylamido)methyl-8-hydroxyquinoline, bis-(5-(acrylamido)methyl-8-hydroxyquinolino) nickel(II) (Ni(AAMQ)₂) has been synthesized and its third-order nonlinear optical properties was investigated with respect to that of bis-(8-hydroxyquinolino) nickel(II) (NiQ₂) by single beam Z-scan technique. The real parts (γ_R) of the molecular second-order hyperpolarizabilities were −6.0 × 10⁻⁴⁶ and −5.5 × 10⁻⁴⁶ m⁵/v² for NiQ₂ and Ni(AAMQ)₂, respectively, indicative of similar nonlinear refraction both in sign and in magnitude. After substitution of an acrylamidomethyl group to the 8-hydroxyquinoline (8-HQ) ligand, the nonlinear absorption coefficient of Ni(AAMQ)₂ was enhanced by more than two times. The corresponding imaginary part (γ_I) of the molecular second-order hyperpolarizability was 3.4 × 10⁻⁴⁶ m⁵/v² for Ni(AAMQ)₂ while 1.6 × 10⁻⁴⁶ m⁵/v² for NiQ₂. The increase in nonlinear absorption was attributed to the substitution effect and the enhanced transition dipole moment due to the participation of δ-donor group of CH₂ in the molecular conjugation.     

Nonlinear optical studies of 1-3-diaryl-propenones containing 4-methylthiophenyl moieties

The third-order nonlinear optical properties of chalcone derivatives have been studied using the single beam Z-scan technique. The dependence of χ⁽³⁾ on different donor and acceptor type substituents demonstrates the electronic nonlinearity of compounds. The largest value of nonlinear refractive index, n₂, measured for a high electron donor substituted molecule is −2.033 × 10⁻¹¹ esu. These molecules exhibit a strong two-photon absorption and interesting optical limiting of nanosecond laser pulses at 532 nm.     

Nonlinear optical absorption studies of an organo-metallic complex by Z-scan technique

An organo-metallic complex, [(CH₃)₄N][Ni(dmit)₂] (dmit²⁻ = (1,3-dithiole-2-thione-4,5-dithiolate), abbreviated as MeNi, is synthesized. The nonlinear optical absorption properties of MeNi dissolved in acetone have been studied using the open-aperture Z-scan technique with 40 ps pulse width at 1064 nm and 1 ns, 15 ns pulse width at 1053 nm, respectively. Strong saturable absorption has been found when the sample solution is irradiated by 40 ps and 1 ns laser pulses. While irradiated with 15 ns laser pulse, a stronger reverse saturable absorption has been found. The nonlinear optical absorption coefficients are −1.03 × 10⁻¹¹ m/W, −1.85 × 10⁻¹¹ m/W and 3.84 × 10⁻¹⁰ m/W, respectively. The mechanism responsible for the difference between the results is analyzed. All the results suggest that this material may be a promising candidate for the application to laser pulse compression in the near-infrared waveband.     

Optical limiting properties of CdS nanowires

Intensity-dependent nonlinear optical transmission studies of cadmium sulfide (CdS) nanowires (∼ 50-100 nm diameter) suspended in dimethylformamide have been carried out in the visible region using the Z-scan technique with 7 ns pulses from the second harmonic of an Nd:YAG laser. The optical limiting threshold of CdS nanowires suspension was determined to be 1.3 J cm^− 2, with normalized transmittance of 0.47, which is relatively lower when compared with those of many popular metal nanowire suspensions reported in the literature. Based on an effective three-photon absorption model, nonlinear absorption and nonlinear scattering were identified as the dominant processes for the measured reduced transmittance.     

3,3′-Benzene-1,4-diylbis[1-(substituted)phenylprop-2-en-1-one] derivatives: A new class of materials for third-order nonlinear optical applications

We have investigated the third-order nonlinear optical parameters of Bischalcones embedded in DMF solution and in solid PMMA matrix, by Z-scan technique using nanosecond laser pulse trains at 532 nm. Z-scan results reveal that the Bischalcones exhibits negative nonlinear refractive index as high as 10⁻¹¹ esu. The molecular two-photon absorption cross-section of Bischalcones were of the order 10⁻⁴⁶ cm⁴ s/photon, which is nearly two orders of magnitude larger than that of Rhodamine 6G which is 10⁻⁴⁸ - 10⁻⁵⁰ cm⁴ s/photon. We found that, the two-photon absorption (TPA) is the dominating nonlinear process leading to nonlinear absorption in both the cases in solution and as well as in solid medium. Based on TPA process, the Bischalcones exhibit good optical power limiting of nanosecond laser pulses at the input wavelength. The nonlinear optical parameters found to increase on enhancing the strength of the electron donor groups indicating the dependence and importance of electron donor/acceptor units on third-order nonlinear optical susceptibility χ⁽³⁾.     

χ measurement and optical limiting studies of urea picrate

The molecular charge complex urea picrate (UP) was synthesized and its third order nonlinear optical properties have been investigated using a single beam Z-scan technique with nanosecond laser pulses at 532 nm. Open aperture data of the compound indicates two photon absorption at this wavelength. The nonlinear refractive index n₂, nonlinear absorption coefficient β, magnitude of effective third order susceptibility χ⁽³⁾, the second order hyperpolarizability γ_h and the coupling factor ρ have been estimated. The experimentally determined values of β, n₂, Re χ⁽³⁾ and Im χ⁽³⁾, γ_h and ρ of the compound UP are 2.146 cm/GW, −1.258×10⁻¹¹ esu, −1.347×10⁻¹³ esu, 0.377×10⁻¹³ esu, 0.69×10⁻³² esu and 0.28, respectively. The compound exhibits good optical limiting at 532 nm with the limiting threshold of 80 μJ/pulse. Our studies suggest that compound UP is a potential candidate for optical device applications such as optical limiters.     

Effect of concentration and particle size on nonlinearity of Au nano-fluid prepared by γ (Co) radiation

Nonlinear properties of Au nano-fluid prepared by γ-radiation method at different concentrations were investigated. Measurements of nonlinear refractive index and nonlinear absorption coefficient were carried out using a single beam Z-scan technique. A green CW laser beam operated at 532 nm was used as excitation source. The Au nano-fluid shows a good third order nonlinear response. The sign of the nonlinear refractive index is found to be negative and the magnitude is in the order of 10⁻⁷ cm²/W. This nonlinear effect increases as the concentration increases from 3.119 × 10⁻⁴ to 2.354 × 10⁻³ M which correspond to particle sizes of 4.0-30.5 nm, respectively. A good linear relationship was obtained between nonlinear refractive index and concentration. However the relationship between nonlinear refractive index and particle size was nonlinear behavior.     

Photophysical and nonlinear optical properties of zincphthalocyanines with peripheral substitutions

Photophysical and nonlinear optical properties of zinc phthalocyanines (ZnPc) bearing peripheral phenoxy substituents containing different functionalized groups were studied. Fluorescence spectra corresponding to the optical transition S₁ → S₀ are found to be appeared at 684 or 686.4 nm. Z-scan technique reveals large nonlinearities, where the absorptive and refractive effects are separately evaluated. Saturation absorption of ZnPc-1 was observed at 632.8 nm, with a very large nonlinear absorption coefficient β = −1.36 × 10⁻² cm/W. However a strong nonlinear refractive effect was found in all ZnPcs (1-4). Transmitted versus incident irradiance measurements carried out on ZnPc-1 and ZnPc-2, showed a very clear optical limiting behavior with irradiance thresholds around be 44 W/cm² and 90 W/cm² respectively.     

Third-order optical nonlinearity of (Ba0.7Sr0.3)TiO3 ferroelectric thin films fabricated by soft solution processing

(Ba_0.7Sr_0.3)TiO₃ (BST) ferroelectric thin films with perovskite crystal structure were fabricated by soft solution processing on a quartz substrate. The third-order nonlinear optical properties were investigated by using Z-scan technique. Positive nonlinear refractive index and nonlinear absorption coefficient were determined to be 4×10⁻⁷ esu and 1.2×10⁻⁶ m/w, respectively. The real part and imaginary part of third-order optical nonlinear susceptibility were calculated and the values were 6.43×10⁻⁸ and 5.14×10⁻⁸ esu, respectively. All of these results show ferroelectric BST thin film is promising for applications in nonlinear optical devices.     

Impedance study of polymethyl methacrylate composites/multi-walled carbon nanotubes (PMMA/MWCNTs)

The dielectric behavior of polymethyl methacrylate/multi-walled carbon nanocomposites (PMMA/MWCNTs) was investigated using impedance spectroscopy technique. The composites were prepared using melt mixing with MWCNTs loading ranging from 0.01 to 10 wt%. The experimental results showed that the measured impedance reflects the insulating behavior of the host material (PMMA) with no appreciable effects of the filler less than 8.5 wt%. However, for the sample containing 10 wt%, the calculated value of dc conductivity increases with increasing temperature from 2.0×10⁻⁶ (Ω m)⁻¹ to attain a value of 4.8×10⁻⁶ (Ω m)⁻¹ at 110 °C. The percolation threshold derived from the dielectric data was estimated to be higher than 8.5 wt% and lower than 10 wt%. A temperature dependent electrical relaxation phenomenon was only observed in the sample containing 10 wt% of MWCNTs. The frequency dependence of the ac conductivity data followed a power law.     

Nonlinear optical properties and photoinduced anisotropy of an azobenzene ionic liquid-crystalline polymer

The nonlinear optical properties and photoinduced anisotropy of an azobenzene ionic liquid-crystalline polymer were investigated. The single beam Z-scan measurement showed the polymer film possessed a value of nonlinear refractive index n₂ = −1.07 × 10⁻⁹ cm²/W under a picosecond 532 nm excitation. Photoinduced anisotropy in the polymer was studied through dichroism and photoinduced birefringence. A photoinduced birefringence value Δn ∼ 10⁻² was achieved in the polymer film. The mechanism for the nonlinear optical response and the physical process of photoinduced anisotropy in the polymer were discussed.     

Investigation of third-order nonlinear optical properties of conjugated benzodioxal derivatives

An investigation of third-order nonlinear optical characterization of newly synthesized conjugated benzodioxal derivatives has been done by using nanosecond Z-scan technique at 532 nm. The molecules demonstrate self-defocusing effect with intensity dependent refractive index (n₂) of the order of 10⁻¹⁴ cm²/W. The measured molecular TPA cross-section is ranging from 2.47 ×10⁻⁴⁷ cm⁴ s/photon to 6.00 cm⁴ s/photon. Their input-output curves indicate that there is a clear optical power limiting behavior with the limiting threshold in the range 125-181 μJ. The main factor to exhibit the observed nonlinearity in these molecules is the presence of charge donor and acceptor groups. The increased conjugation length increases the nonlinear refraction and increased electron density enhances the nonlinear absorption. The molecules exhibit good nonlinear optical properties, comparable to those of regular azoaromatic compounds. Therefore, the molecules investigated here are promising candidates for optical power limiting devices.     

Optical characterization of CdS semiconductor nanoparticles capped with starch

Starch capped cadmium sulfide (CdS) nanoparticles were synthesized by aqueous solution precipitation. Starch added during the synthesis of nanoparticles resulted in cadmium-rich nanoparticles forming a stable complex with starch. The size of the CdS quantum dots was measured using high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). The average diameter (d) of nanoparticles spanned the range 4.8 ± 0.4 to 5.7 ± 0.2 nm when the pH of the solution was varied within the range 10-14. The main Raman phonon of CdS, the longitudinal optical mode located around 300 cm⁻¹, softens as diameter decreases, in accordance with theoretical predictions. In addition, the largest Raman response of starch, near 478 cm⁻¹, related with the important skeletal vibration modes of the starch pyranose ring, dominates the spectra of the CdS capped nanoparticles and also softens as the size decreases. This fact indicates a strain variation on CdS as a function of d which increases as the pH increases.