Diagnostic study of the roughness surface effect of zirconium on the third-order nonlinear-optical properties of thin films based on zinc oxide nanomaterials

Zinc oxide (ZnO) and zirconium doped zinc oxide (ZnO:Zr) thin films were deposited by reactive chemical pulverization spray pyrolysis technique on heated glass substrates at 500 °C using zinc and zirconium chlorides as precursors. Effects of zirconium doping agent and surface roughness on the nonlinear optical properties were investigated in detail using atomic force microscopy (AFM) and third harmonic generation (THG) technique. The best value of nonlinear optical susceptibility χ⁽³⁾ was obtained from the doped films with less roughness. A strong third order nonlinear optical susceptibility χ⁽³⁾ = 20.12 × 10⁻¹² (esu) of the studied films was found for the 3% doped sample.     

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.     

Nonlinear optical properties of Au/ZnO nanoparticle arrays

The triangular-shaped Au/ZnO nanoparticle arrays were fabricated on fused quartz substrate using nanosphere lithography. The structural characterization of the Au/ZnO nanoparticle arrays was investigated by atomic force microscopy. The absorption peak due to the surface plasmon resonance of Au particles at the wavelength of about 570 nm was observed. The nonlinear optical properties of the nanoparticle arrays were measured using the z-scan method at a wavelength of 532 nm with pulse duration of 10 ns. The real and imaginary part of third-order nonlinear optical susceptibility, Re χ⁽³⁾ and Im χ⁽³⁾, were determined to be 1.15 × 10⁻⁶ and −5.36 × 10⁻⁷ esu, respectively. The results show that the Au/ZnO nanoparticle arrays have great potential for future optical devices.     

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.     

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.     

Comparative analysis of multi-wave mixing and measurements of the higher-order nonlinearities in resonant media

The features of degenerate multi-wave mixing in resonant media (dye solutions) have been studied theoretically and experimentally. It has been demonstrated that thermal nonlinearity due to the induced absorption from the excited level contributes significantly to the efficiency of four-wave mixing, but results in lower efficiency of higher-order interactions. The measurement results obtained for the energy efficiency of four-, six- and eight-wave mixing enable calculations of the third-, fifth- and seventh-order nonlinear optical susceptibilities, respectively. Experimentally, the method proposed for measurements of the higher-order nonlinearities has been realized with the use of the multi-wave mixing at second harmonic λ = 532 nm of monopulse YAG:Nd³⁺ laser radiation in a Rhodamine 6G dye solution. The ratios ∣χ⁽⁵⁾∣/∣χ⁽³⁾∣ and ∣χ⁽⁷⁾∣/∣χ⁽⁵⁾∣ are determined to be of the order of 10⁻⁵ cm³/erg.     

Influence of the central metal atom on the nonlinear optical properties of MPcs solutions and thin films

Third order nonlinear optical susceptibility (χ^〈3〉) of metallophthalocyanines (MPcs, where M = Co, Cu, Zn, Mg) thin films and solutions was investigated by standard backward degenerate four wave mixing (DFWM) method at 532 nm. Third harmonic generation (THG) measurement at 1064 nm performed on MPcs thin films is also discussed. MPcs thin films were grown by conventional thermal evaporation in high vacuum and solution were dissolved in tetrahydrofuran (THF), in which the studied materials are soluble. In the case of microscopic nonlinearity, we calculated the second order hyperpolarizability (γ) for MPcs solutions. We found that the χ^〈3〉 and the γ values are affected by the nature of the central metal atom. We also found that the value is larger than that measured via THG experiment. The variation in χ^〈3〉 values occurs due to the different resonance contributions.     

Second-harmonic generation in the thermal/electrical poling (100−x)GeS2·x(0.5Ga2S3·0.5CdS) chalcogenide glasses

Utilizing Maker fringe (MF) method, second-harmonic generation (SHG) has been observed within the GeS₂-Ga₂S₃-CdS pseudo-ternary glasses through thermal/electrical poling technique. The SHG phenomenon was considered to be the result of breakage of the glassy macroscopic isotropy originated from the reorientations of dipoles during the thermal/electrical poling process. Under the same poling condition conducted with 5 kV and 280 °C for 30 min, the maximum value of second-order nonlinear susceptibility χ⁽²⁾ of the poled (100−x)GeS₂·x(0.5Ga₂S₃·0.5CdS) glasses was obtained to be ≈4.36 pm/V when the value of x is equal to 30. Nonlinear dependence of χ⁽²⁾ on compositions of these glasses can be well explained according to the theory related to the reorientation of dipoles.     

Femtosecond Z-scan measurement of third-order optical nonlinearities in anatase TiO2 thin films

Anatase phase TiO₂ films have been grown on fused silica substrate by pulsed laser deposition technique at substrate temperature of 750 °C under the oxygen pressure of 5 Pa. From the transmission spectra, the optical band gap and linear refractive index of the TiO₂ films were determined. The third-order optical nonlinearities of the films were measured by Z-scan method using a femtosecond laser (50 fs) at the wavelength of 800 nm. The real and imaginary parts of third-order nonlinear susceptibility χ⁽³⁾ were determined to be −7.1 × 10⁻¹¹esu and −4.42 × 10⁻¹²esu, respectively. The figure of merit, T, defined by T=βλ/n₂, was calculated to be 0.8, which meets the requirement of all-optical switching devices. The results show that the anatase TiO₂ films have great potential applications for nonlinear optical devices.     

Third-order nonlinear optical properties of thin sputtered gold films

Au films of thickness ranging between 5 and 52 nm were prepared by sputtering on quartz substrates and their third-order nonlinear optical response was investigated by Optical Kerr effect (OKE) and Z-scan techniques using 532 nm, 35 ps laser pulses. All prepared films were characterized by XRD, AFM and UV-VIS-NIR spectrophotometry while their third-order susceptibility χ⁽³⁾ was measured and found to be of the order of 10⁻⁹ esu. The real and imaginary parts of the third-order susceptibility were found in very good agreement with experimental results and theoretical predictions reported by Smith et al. [D.D. Smith, Y. Yoon, R.W. Boyd, Y.K. Cambell, L.A. Baker, R.M. Crooks, M. George, J. Appl. Phys. 86 (1999) 6200].     

Synthesis of CdZnO thin film as a potential candidate for optical switches

Cadmium doped zinc oxide thin films have been prepared using a thermal decomposition technique. The influence of Cd as a doping agent on the structure, optical and nonlinear optical properties was carefully investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM) and a UV-vis spectrophotometer. A deep correlation has been found between the surface roughness and the optical properties. The roughness is found to deteriorate the nonlinear response, such that the highest nonlinear susceptibility χ⁽³⁾ is obtained for the smoothest layer. The third-order nonlinear susceptibility χ⁽³⁾ has been calculated using the Frumer model, and is estimated to be 3.37×10⁻¹⁰ esu. The dispersion of the refractive index of the prepared thin film is shown to follow the single electronic oscillator model. From the model, the values of oscillator strength (E_d), oscillator energy (E_o) and dielectric constant (ε_∞) have been determined. The conductivity has been measured as a function of the energy of the photons, revealing marginal change at energies below 3.15 eV, while above this value there is a large increase in the conductivity. This suggests that CdZnO is a potential candidate for applications in optical devices such as optical limiter and optical switching.     

Z-scan measurements of optical nonlinearity in acid blue 29 dye

The third order nonlinear optical properties of acid blue 29 solutions have been studied using Z-scan technique. Experiments are performed using a CW He–Ne laser at 632.8 nm wavelength and 3 mW power. The linear absorption coefficient α₀, nonlinear absorption coefficient β, nonlinear refractive index n₂, Re χ³, and Im χ³ are measured at three different concentrations. Our results show that higher concentration gives better nonlinear optical properties. Also, it was found that there is an increasing trend in the value of the nonlinear refractive index n₂ as the concentration increases.     

Enhanced nonlinear optical responses in metal-glass nanocomposites

The “engineered” nonlinear nanocomposite materials with extremely large values of optical Kerr susceptibility and fast temporal responses that can be precisely tuned to satisfy the requirements of switching applications is of current interest in photonics. Metal quantum-dot composite glasses can exhibit enhanced optical susceptibility, χ⁽³⁾, whose real and imaginary parts are related to the intensity-dependent refractive index and two-photon absorption coefficient, respectively. Classical (dielectric) and quantum confinement effects come into play in the nonlinear optical responses of these nanocomposites. Metal nanocluster-glass composites have been synthesized by 200 keV Cu⁺ and 1.5 MeV Au⁺ ion implantations in fused silica glasses at a dose of 3 × 10¹⁶ ions/cm², followed by thermal annealing in reducing atmosphere to promote cluster growth. UV-Visible spectroscopy has revealed prominent linear absorption bands at characteristic surface plasmon resonance (SPR) frequencies signifying appreciable formation of copper and gold colloids in glass matrices. Third-order optical properties of the composite materials have been studied by Z-Scan and Anti-Resonant Interferometric Nonlinear Spectroscopy (ARINS) measurements. The sign of nonlinear refraction is readily obtained from the Z-Scan signatures. The ARINS technique utilizes the dressing of two unequal-intensity counter-propagating pulsed light beams with differential nonlinear phases, which occur upon traversing the sample if it exhibits nonlinear optical response. This difference in phase manifests itself in the intensity-dependent transmission. The nonlinear refractive index, nonlinear absorption coefficient, the real and imaginary parts of the third-order optical susceptibility have been extracted.     

Nonlinear optical studies of a newly synthesized copolymer containing oxadiazole and substituted thiophenes

We investigated the third-order nonlinear optical properties of a newly synthesized soluble copolymer containing oxadiazole and thiophene units using Z-scan and Degenerate Four Wave Mixing (DFWM) techniques. The measurements were performed at 532 nm with 7 ns pulses from a Nd:YAG laser. We found a good agreement between the values of χ⁽³⁾ determined from both experiments. Z-scan results indicate a negative nonlinear refractive index, n₂, whose magnitude is of the order of 10⁻¹⁰ esu. The copolymer exhibits strong nonlinear absorption and good optical limiting properties at 532 nm, and hence may be a potential material for optical limiting applications.     

Synthesis, characterization and studies on the nonlinear optical parameters of hydrazones

Three hydrazones, 2-(4-methylphenoxy)-N′-[(1E)-(4-nitrophenyl)methylene]acetohydrazide (compound-1), 2-(4-methylphenoxy)-N′-[(1E)-(4-methylphenyl)methylene]acetohydrazide ((compound-2) and N′-{(1E)-[4-(dimethylamino)phenyl]methylene}-2-(4-ethylphenoxy) acetohydrazide(compound-3) were synthesized and their third order nonlinear optical properties were investigated using a single beam z-scan technique with nanosecond laser pulses at 532 nm. Open aperture data obtained from the three compounds indicates two photon absorption at this wavelength. The nonlinear refractive index n₂, the nonlinear absorption coefficient β, the magnitude of the effective third order susceptibility χ⁽³⁾, the second order hyperpolarizability γ_h and the coupling factor ρ have been estimated. The values obtained are comparable with the values obtained for 4-methoxy chalcone derivatives and dibenzylidene acetone derivatives. Among the compounds studied, compounds-1 and 3 exhibited the better optical power limiting behaviour at 532 nm. Our studies suggest that compounds-1, 2 and 3 are potential candidates for optical device applications such as optical limiters and optical switches.     

Nonlinear optical properties and phase-relaxation processes in single-walled carbon nanotubes

We have investigated third-order nonlinear optical properties of bundled and isolated semiconducting single-walled carbon nanotubes (SWNTs) by means of Z-scan method, pump-probe method, and two-beam time-resolved degenerate four-wave mixing (DFWM) method. The figures of merit Im χ⁽³⁾/α in both bundled and isolated SWNTs samples were found to be enhanced with increasing tube diameter. The measured Im χ⁽³⁾/α value in the bundled SWNTs was an order of magnitude smaller than that in the isolated SWNTs. Both population relaxation time T₁ and phase-relaxation time T₂ for bundled samples were smaller than those in the isolated samples. These experimental results can be explained by an increase in nonradiative recombination rate and phase-relaxation rate in the bundled sample. The phase-relaxation time T₂ is considered to have a significant role in the enhancement of Im χ⁽³⁾/α.     

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.     

Magnetic anomalies in single crystalline ErPd2Si2

Considering certain interesting features in the previously reported ¹⁶⁶Er Mössbauer effect, and neutron diffraction data on the polycrystalline form of ErPd₂Si₂ crystallizing in the ThCr₂Si₂-type tetragonal structure, we have carried out magnetic measurements (1.8–300 K) on the single crystalline form of this compound. We observe significant anisotropy in the absolute values of magnetization (indicating that the easy axis is c-axis) as well as in features due to magnetic ordering in the plot of magnetic susceptibility χ versus temperature T at low temperatures. The χ(T) data reveal that there is a pseudo-low-dimensional magnetic order setting in at 4.8 K, with a three-dimensional antiferromagnetic order setting in at a lower temperature (3.8 K). A new finding in the χ(T) data is that, for H∥〈1 1 0〉 but not for H∥〈0 0 1〉, there is a broad shoulder in the range 8–20 K, indicative of the existence of magnetic correlations above 5 K as well, which could be related to the previously reported slow-relaxation-dominated Mössbauer spectra. Interestingly, the temperature coefficient of electrical resistivity is found to be isotropic; no feature due to magnetic ordering could be detected in the electrical resistivity data at low temperatures, which is attributed to magnetic Brillioun-zone boundary gap effects. The results reveal the complex nature of magnetism of this compound.     

Organic thin films based on a dicyanovinyl-quaterthiophene: Influence of electrode configuration on third-order nonlinear optical properties measured by electroabsorption spectroscopy

Electroabsorption (EA) studies at room temperature on organic thin films based on a dicyanovinyl-quaterthiophene 4T-V(CN)₂ are reported. An electric field modulation is applied to the samples for two different electrode geometries, i.e. sandwich and coplanar versus the organic layer. Changes in optical absorption coefficient of 4T-V(CN)₂ based thin films are measured and analyzed to determine the character of the optical transition in the visible range (400-800 nm). Depending on the experimental electrode configuration, magnitude of electroabsorption responses are different, possibly due to different distribution of the externally applied electric field. The results indicate a higher resolution of EA response for the sandwich electrode configuration and confirm the charge transfer exciton character of 4T-V(CN)₂ in contrast to the unsubstituted quaterthiophene 4T. Finally, a third-order nonlinear susceptibility χ⁽³⁾ (−ω; ω, 0, 0) of 16 × 10⁻¹² e.s.u. is obtained.     

Third-order nonlinear optical studies of new anthraquinone derivatives

Four new donor-acceptor-donor anthraquinone derivatives were synthesized and characterized by UV, IR, ¹H NMR and elemental analysis. Their off-resonant third-order nonlinear optical properties were measured using femtosecond laser and degenerate four-wave mixing technique. The third-order nonlinear optical susceptibilities χ⁽³⁾ were 3.36-3.76 × 10⁻¹³ esu. The nonlinear refractive indexes n₂ were 6.19-6.91 × 10⁻¹² esu. The second-order hyperpolarizabilities γ of the molecules were 3.36-3.76 × 10⁻³¹ esu. The response times were 101-115 fs. The results show that these compounds have potential nonlinear optical applications.