Third order nonlinear optical studies in europium naphthalocyanine using degenerate four wave mixing and Z-scan

Third order nonlinear susceptibility χ(3) and second hyperpolarizability (γ) of a bis-naphthalocyanine viz. europium naphthalocyanines, Eu(Nc)2, were measured in dimethyl formamide solution using degenerate four wave mixing at 532 nm under nanosecond pulse excitation. Effective nonlinear absorption coefficient, βeff and imaginary part of nonlinear susceptibility, Im(χ(3)) were obtained using open aperture /Z-scan technique at the same wavelength. Optical limiting property of the sample was also investigated. The role of excited state absorption in deciding the nonlinear properties of this material is discussed.

Spectral dependence of third order nonlinear optical susceptibility of zinc phthalocyanine

Wavelength dependence of saturable absorption (SA) and reverse saturable absorption (RSA) of zinc phthalocyanine was studied using 10 Hz, 8 ns pulses from a tunable laser, in the wavelength range of 520–686 nm, which includes the rising edge of the Q band in the electronic absorption spectrum. The nonlinear response is wavelength dependent and switching from RSA to SA has been observed as the excitation wavelength changes from the low absorption window region to higher absorption regime near the Q band. The SA again changes back to RSA when we further move over to the infrared region. Values of the imaginary part of third order susceptibility are calculated for various wavelengths in this range. This study is important in identifying the spectral range over which the nonlinear material acts as RSA based optical limiter.

Spectral dependence of third order nonlinear optical susceptibility of zinc phthalocyanine

Wavelength dependence of saturable absorption (SA) and reverse saturable absorption (RSA) of zinc phthalocyanine was studied using 10 Hz, 8 ns pulses from a tunable laser, in the wavelength range of 520–686 nm, which includes the rising edge of the Q band in the electronic absorption spectrum. The nonlinear response is wavelength dependent and switching from RSA to SA has been observed as the excitation wavelength changes from the low absorption window region to higher absorption regime near the Q band. The SA again changes back to RSA when we further move over to the infrared region. Values of the imaginary part of third order susceptibility are calculated for various wavelengths in this range. This study is important in identifying the spectral range over which the nonlinear material acts as RSA based optical limiter.

Synthesis, Characterization and Applications of Modified TiO2 Systems

This thesis is divided in to 9 chapters and deals with the modification of TiO2 for various applications include photocatalysis, thermal reaction, photovoltaics and non-linear optics. Chapter 1 involves a brief introduction of the topic of study. An introduction to the applications of modified titania systems in various fields are discussed concisely. Scope and objectives of the present work are also discussed in this chapter. Chapter 2 explains the strategy adopted for the synthesis of metal, nonmetal co-doped TiO2 systems. Hydrothermal technique was employed for the preparation of the co-doped TiO2 system, where Ti[OCH(CH3)2]4, urea and metal nitrates were used as the sources for TiO2, N and metals respectively. In all the co-doped systems, urea to Ti[OCH(CH3)2]4 was taken in a 1:1 molar ratio and varied the concentration of metals. Five different co-doped catalytic systems and for each catalysts, three versions were prepared by varying the concentration of metals. A brief explanation of physico-chemical techniques used for the characterization of the material was also presented in this chapter. This includes X-ray Diffraction (XRD), Raman Spectroscopy, FTIR analysis, Thermo Gravimetric Analysis, Energy Dispersive X-ray Analysis (EDX), Scanning Electron Microscopy(SEM), UV-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS), Transmission Electron Microscopy (TEM), BET Surface Area Measurements and X-ray Photoelectron Spectroscopy (XPS). Chapter 3 contains the results and discussion of characterization techniques used for analyzing the prepared systems. Characterization is an inevitable part of materials research. Determination of physico-chemical properties of the prepared materials using suitable characterization techniques is very crucial to find its exact field of application. It is clear from the XRD pattern that photocatalytically active anatase phase dominates in the calcined samples with peaks at 2θ values around 25.4°, 38°, 48.1°, 55.2° and 62.7° corresponding to (101), (004), (200), (211) and (204) crystal planes (JCPDS 21-1272) respectively. But in the case of Pr-N-Ti sample, a new peak was observed at 2θ = 30.8° corresponding to the (121) plane of the polymorph brookite. There are no visible peaks corresponding to dopants, which may be due to their low concentration or it is an indication of the better dispersion of impurities in the TiO2. Crystallite size of the sample was calculated from Scherrer equation byusing full width at half maximum (FWHM) of the (101) peak of the anatase phase. Crystallite size of all the co-doped TiO2 was found to be lower than that of bare TiO2 which indicates that the doping of metal ions having higher ionic radius into the lattice of TiO2 causes some lattice distortion which suppress the growth of TiO2 nanoparticles. The structural identity of the prepared system obtained from XRD pattern is further confirmed by Raman spectra measurements. Anatase has six Raman active modes. Band gap of the co-doped system was calculated using Kubelka-Munk equation and that was found to be lower than pure TiO2. Stability of the prepared systems was understood from thermo gravimetric analysis. FT-IR was performed to understand the functional groups as well as to study the surface changes occurred during modification. EDX was used to determine the impurities present in the system. The EDX spectra of all the co-doped samples show signals directly related to the dopants. Spectra of all the co-doped systems contain O and Ti as the main components with low concentrations of doped elements. Morphologies of the prepared systems were obtained from SEM and TEM analysis. Average particle size of the systems was drawn from histogram data. Electronic structures of the samples were identified perfectly from XPS measurements. Chapter 4 describes the photocatalytic degradation of herbicides Atrazine and Metolachlor using metal, non-metal co-doped titania systems. The percentage of degradation was analyzed by HPLC technique. Parameters such as effect of different catalysts, effect of time, effect of catalysts amount and reusability studies were discussed. Chapter 5 deals with the photo-oxidation of some anthracene derivatives by co-doped catalytic systems. These anthracene derivatives come underthe category of polycyclic aromatic hydrocarbons (PAH). Due to the presence of stable benzene rings, most of the PAH show strong inhibition towards biological degradation and the common methods employed for their removal. According to environmental protection agency, most of the PAH are highly toxic in nature. TiO2 photochemistry has been extensively investigated as a method for the catalytic conversion of such organic compounds, highlighting the potential of thereof in the green chemistry. There are actually two methods for the removal of pollutants from the ecosystem. Complete mineralization is the one way to remove pollutants. Conversion of toxic compounds to another compound having toxicity less than the initial starting compound is the second way. Here in this chapter, we are concentrating on the second aspect. The catalysts used were Gd(1wt%)-N-Ti, Pd(1wt%)-N-Ti and Ag(1wt%)-N-Ti. Here we were very successfully converted all the PAH to anthraquinone, a compound having diverse applications in industrial as well as medical fields. Substitution of 10th position of desired PAH by phenyl ring reduces the feasibility of photo reaction and produced 9-hydroxy 9-phenyl anthrone (9H9PA) as an intermediate species. The products were separated and purified by column chromatography using 70:30 hexane/DCM mixtures as the mobile phase and the resultant products were characterized thoroughly by 1H NMR, IR spectroscopy and GCMS analysis. Chapter 6 elucidates the heterogeneous Suzuki coupling reaction by Cu/Pd bimetallic supported on TiO2. Sol-Gel followed by impregnation method was adopted for the synthesis of Cu/Pd-TiO2. The prepared system was characterized by XRD, TG-DTG, SEM, EDX, BET Surface area and XPS. The product was separated and purified by column chromatography using hexane as the mobile phase. Maximum isolated yield of biphenyl of around72% was obtained in DMF using Cu(2wt%)-Pd(4wt%)-Ti as the catalyst. In this reaction, effective solvent, base and catalyst were found to be DMF, K2CO3 and Cu(2wt%)-Pd(4wt%)-Ti respectively. Chapter 7 gives an idea about the photovoltaic (PV) applications of TiO2 based thin films. Due to energy crisis, the whole world is looking for a new sustainable energy source. Harnessing solar energy is one of the most promising ways to tackle this issue. The present dominant photovoltaic (PV) technologies are based on inorganic materials. But the high material, low power conversion efficiency and manufacturing cost limits its popularization. A lot of research has been conducted towards the development of low-cost PV technologies, of which organic photovoltaic (OPV) devices are one of the promising. Here two TiO2 thin films having different thickness were prepared by spin coating technique. The prepared films were characterized by XRD, AFM and conductivity measurements. The thickness of the films was measured by Stylus Profiler. This chapter mainly concentrated on the fabrication of an inverted hetero junction solar cell using conducting polymer MEH-PPV as photo active layer. Here TiO2 was used as the electron transport layer. Thin films of MEH-PPV were also prepared using spin coating technique. Two fullerene derivatives such as PCBM and ICBA were introduced into the device in order to improve the power conversion efficiency. Effective charge transfer between the conducting polymer and ICBA were understood from fluorescence quenching studies. The fabricated Inverted hetero junction exhibited maximum power conversion efficiency of 0.22% with ICBA as the acceptor molecule. Chapter 8 narrates the third order order nonlinear optical properties of bare and noble metal modified TiO2 thin films. Thin films were fabricatedby spray pyrolysis technique. Sol-Gel derived Ti[OCH(CH3)2]4 in CH3CH2OH/CH3COOH was used as the precursor for TiO2. The precursors used for Au, Ag and Pd were the aqueous solutions of HAuCl4, AgNO3 and Pd(NO3)2 respectively. The prepared films were characterized by XRD, SEM and EDX. The nonlinear optical properties of the prepared materials were investigated by Z-Scan technique comprising of Nd-YAG laser (532 nm,7 ns and10 Hz). The non-linear coefficients were obtained by fitting the experimental Z-Scan plot with the theoretical plots. Nonlinear absorption is a phenomenon defined as a nonlinear change (increase or decrease) in absorption with increasing of intensity. This can be mainly divided into two types: saturable absorption (SA) and reverse saturable absorption (RSA). Depending on the pump intensity and on the absorption cross- section at the excitation wavelength, most molecules show non- linear absorption. With increasing intensity, if the excited states show saturation owing to their long lifetimes, the transmission will show SA characteristics. Here absorption decreases with increase of intensity. If, however, the excited state has strong absorption compared with that of the ground state, the transmission will show RSA characteristics. Here in our work most of the materials show SA behavior and some materials exhibited RSA behavior. Both these properties purely depend on the nature of the materials and alignment of energy states within them. Both these SA and RSA have got immense applications in electronic devices. The important results obtained from various studies are presented in chapter 9.

Effect of annealing on the spectral and nonlinear optical characteristics of thin films of nano-ZnO

The annealing effect on the spectral and nonlinear optical NLO characteristics of ZnO thin films deposited on quartz substrates by sol-gel process is investigated. As the annealing temperature increases from 300–1050 °C, there is a decrease in the band gap, which indicates the changes of the interface of ZnO. ZnO is reported to show two emission bands, an ultraviolet UV emission band and another in the green region. The intensity of the UV peak remains the same while the intensity of the visible peak increases with increase in annealing temperature. The role of oxygen in ZnO thin films during the annealing process is important to the change in optical properties. The mechanism of the luminescence suggests that UV luminescence of ZnO thin films is related to the transition from conduction band edge to valence band, and green luminescence is caused by the transition from deep donor level to valence band due to oxygen vacancies. The NLO response of these samples is studied using nanosecond laser pulses at off-resonance wavelengths. The nonlinear absorption coefficient increases from 2.9 ×10−6 to 1.0 ×10−4 m/W when the annealing temperature is increased from 300 to 1050 °C, mainly due to the enhancement of interfacial state and exciton oscillator strength. The third order optical susceptibility x(3) increases with increase in annealing temperature (T) within the range of our investigations. In the weak confinement regime, T2.4 dependence of x(3) is obtained for ZnO thin films. The role of annealing temperature on the optical limiting response is also studied.

Nonlinear optical characteristics of self-assembled films of ZnO

In the present work, we have investigated the nonlinear optical properties of self-assembled films formed from ZnO colloidal spheres by z-scan technique. The sign of the nonlinear component of refractive index of the material remains the same; however, a switching from reverse saturable absorption to saturable absorption has been observed as the material changes from colloid to self-assembled film. These different nonlinear characteristics can be mainly attributed to ZnO defect states and electronic effects when the colloidal solution is transformed into self-assembled monolayers. We investigated the intensity, wavelength and size dependence of saturable and reverse saturable absorption of ZnO self-assembled films and colloids. Values of the imaginary part of third-order susceptibility are calculated for particles of size in the range 20–300 nm at different intensity levels ranging from 40 to 325MW/cm2 within the wavelength range of 450–650 nm.

Spectral and nonlinear optical characterization of ZnO nanocomposites

The spectral and nonlinear optical characteristics of nano ZnO and its composites are investigated. The fluorescence behaviour of nano colloids of ZnO has been studied as a function of the excitation wavelength and there is a red shift in emission peak with excitation wavelength. Apart from the observation of the reported ultra violet and green emissions, our results reveal that additional blue emissions at 420 nm and 490 nm are developed with increasing particle size. Systematic studies on nano ZnO have indicated the presence of luminescence due to excitonic emissions when excited with 255 nm as well as significant contribution from surface defect states when excited with 325 nm. In the weak confinement regime, the third-order optical susceptibility χ(3) increases with increasing particle size (R) and annealing temperature (T) and a R2 and T2.5 dependence of χ(3) is obtained for nano ZnO. ZnO nanocolloids exhibit induced absorption whereas the self assembled films of ZnO exhibit saturable absorption due to saturation of linear absorption of ZnO defect states and electronic effects. ZnO nanocomposites exhibit negative nonlinear index of refraction which can be attributed to two photon absorption followed by weak free carrier absorption. The increase of the third-order nonlinearity in the composites can be attributed to the enhancement of exciton oscillator strength. The nonlinear response of ZnO nanocomposites is wavelength dependent and switching from induced absorption to saturable absorption has been observed at resonant wavelengths. Such a change-over is related to the interplay of plasmon/exciton band bleach and optical limiting mechanisms. This study is important in identifying the spectral range and the composition over which the nonlinear material acts as an optical limiter. ZnO based nanocomposites are potential materials for enhanced and tunable light emission and for the development of nonlinear optical devices with a relatively small optical limiting threshold.

The tautomerism, solvatochromism and non-linear optical properties of fluorescent 3-hydroxyquinoxaline-2-carboxalidine-4-aminoantipyrine

The Schiff base, 3-hydroxyquinoxaline-2-carboxalidine-4-aminoantipyrine, was synthesized by the condensation of 3-hydroxyquinoxaline-2-carboxaldehyde with 4-aminoantipyrine. HPLC, FT-IR and NMR spectral data revealed that the compound exists predominantly in the amide tautomeric form and exhibits both absorption and fluorescence solvatochromism, large stokes shift, two electron quasireversible redox behaviour and good thermal stability, with a glass transition temperature of 104oC. The third-order non-linear optical character was studied using open aperture Z-scan methodology employing 7 ns pulses at 532 nm. The third-order non-linear absorption coefficient, b, was 1.48 x 10-6 cm W-1 and the imaginary part of the third-order non-linear optical susceptibility, Im c(3), was 3.36 x10-10 esu. The optical limiting threshold for the compound was found to be 340 MW cm-2.

The tautomerism, solvatochromism and non-linear optical properties of fluorescent 3-hydroxyquinoxaline-2-carboxalidine-4-aminoantipyrine

The Schiff base, 3-hydroxyquinoxaline-2-carboxalidine-4-aminoantipyrine, was synthesized by the condensation of 3-hydroxyquinoxaline-2-carboxaldehyde with 4-aminoantipyrine. HPLC, FT-IR and NMR spectral data revealed that the compound exists predominantly in the amide tautomeric form and exhibits both absorption and fluorescence solvatochromism, large stokes shift, two electron quasireversible redox behaviour and good thermal stability, with a glass transition temperature of 104 oC. The third-order non-linear optical character was studied using open aperture Z-scan methodology employing 7 ns pulses at 532 nm. The third-order non-linear absorption coefficient, b, was 1.48 x 10-6 cm W-1 and the imaginary part of the third-order non-linear optical susceptibility, Im c(3), was 3.36x10-10 esu. The optical limiting threshold for the compound was found to be 340 MW cm-2.

Spectral and Nonlinear Optical Characteristics of ZnO Nanocomposites

The spectral and nonlinear optical properties of ZnO based nanocomposites prepared by colloidal chemical synthesis are investigated. Very strong UV emissions are observed from ZnO–Ag, ZnO– Cu and ZnO–SiO2 nanocomposites. The strongest visible emission of a typical ZnO–Cu nanocomposite is over ten times stronger than that of pure Cu due to transition from deep donor level to the copper induced level. The optical band gap of ZnO–CdS and ZnO–TiO2 nanocomposites is tunable and emission peaks changes almost in proportion to changes in band gap. Nonlinear optical response of these nanocomposites is studied using nanosecond laser pulses from a tunable laser in the wavelength range of 450–650 nm at resonance and off-resonance wavelengths. The nonlinear response is wavelength dependent and switching from RSA to SA has been observed at resonant wavelengths. Such a change-over is related to the interplay of plasmon/exciton band bleach and optical limiting mechanisms. The observed nonlinear absorption is explained through two photon absorption followed by weak free carrier absoption, interband absorption and nonlinear scattering mechanisms. The nonlinearity of the silica colloid is low and its nonlinear response can be improved by making composites with ZnO and ZnO–TiO2. The increase of the third-order nonlinearity in the composites can be attributed to the enhancement of exciton oscillator strength. This study is important in identifying the spectral range and the composition over which the nonlinear material acts as an RSA based optical limiter. These nanocomposites can be used as optical limiters and are potential materials for the light emission and for the development of nonlinear optical devices with a relatively small limiting threshold.

Spectral and Nonlinear Optical Characteristics of ZnO Nanocomposites

The spectral and nonlinear optical properties of ZnO based nanocomposites prepared by colloidal chemical synthesis are investigated. Very strong UV emissions are observed from ZnO–Ag, ZnO– Cu and ZnO–SiO2 nanocomposites. The strongest visible emission of a typical ZnO–Cu nanocomposite is over ten times stronger than that of pure Cu due to transition from deep donor level to the copper induced level. The optical band gap of ZnO–CdS and ZnO–TiO2 nanocomposites is tunable and emission peaks changes almost in proportion to changes in band gap. Nonlinear optical response of these nanocomposites is studied using nanosecond laser pulses from a tunable laser in the wavelength range of 450–650 nm at resonance and off-resonance wavelengths. The nonlinear response is wavelength dependent and switching from RSA to SA has been observed at resonant wavelengths. Such a change-over is related to the interplay of plasmon/exciton band bleach and optical limiting mechanisms. The observed nonlinear absorption is explained through two photon absorption followed by weak free carrier absoption, interband absorption and nonlinear scattering mechanisms. The nonlinearity of the silica colloid is low and its nonlinear response can be improved by making composites with ZnO and ZnO–TiO2. The increase of the third-order nonlinearity in the composites can be attributed to the enhancement of exciton oscillator strength. This study is important in identifying the spectral range and the composition over which the nonlinear material acts as an RSA based optical limiter. These nanocomposites can be used as optical limiters and are potential materials for the light emission and for the development of nonlinear optical devices with a relatively small limiting threshold.

Spectral and nonlinear optical characteristics of nanocomposites of ZnO-CdS

In this article, we present the spectral and nonlinear optical properties of ZnO–CdS nanocomposites prepared by colloidal chemical synthesis. The optical band gap (Eg) of the material is tunable between 2.62 and 3.84 eV. The emission peaks of ZnO–CdS nanocomposites change from 385 to 520 nm almost in proportion to changes in Eg. It is possible to obtain a desired luminescence color from UV to green by simply adjusting the composition. The nonlinear optical response of these samples is studied by using nanosecond laser pulses from a tunable laser at the excitonic resonance and off-resonance wavelengths. The nonlinear response is wavelength dependent, and switching from saturable absorption (SA) to reverse SA (RSA) has been observed for samples as the excitation wavelength changes from the excitonic resonance to off-resonance wavelengths. Such a changeover in the sign of the nonlinearity of ZnO–CdS nanocomposites is related to the interplay of exciton bleach and optical limiting mechanisms. The ZnO–CdS nanocomposites show self-defocusing nonlinearity and good nonlinear absorption behavior at off-resonant wavelengths. The nonlinear refractive index and the nonlinear absorption increase with increasing CdS volume fraction at 532 nm. The observed nonlinear absorption is attributed to two photon absorption followed by weak free carrier absorption. The enhancement of the third-order nonlinearity in the composites can be attributed to the concentration of exciton oscillator strength. This study is important in identifying the spectral range and composition over which the nonlinear material acts as a RSA based optical limiter. ZnO–CdS is a potential nanocomposite material for the tunable light emission and for the development of nonlinear optical devices with a relatively small limiting threshold.

Degenerate four wave mixing in some metal phthalocyanines and naphthalocyanines

Here we report measurements of third-order susceptibility χ(3), figure of merit F defined as χ(3)/α (where α is the absorption coefficient) and second hyperpolarizability 〈γ〉 of some metal substituted phthalocyanines and a naphthalocyanine in solutions of dimethyl formamide using degenerate four wave mixing at 532 nm under nanosecond excitation. It was found that among samples investigated, bis-naphthalocyanine possessed the highest value of 〈γ〉 followed by the bis-phthalocyanine. This observation is explained on the basis that bis-naphthalocyanine followed by bis-phthalocyanine has higher degree of π electron conjugation.

Effect of self assembly on the nonlinear optical characteristics of ZnO thin films

In the present work, we report the third order nonlinear optical properties of ZnO thin films deposited using self assembly, sol gel process as well as pulsed laser ablation by z scan technique. ZnO thin films clearly exhibit a negative nonlinear index of refraction at 532 nm and the observed nonlinear refraction is attributed to two photon absorption followed by free carrier absorption. Although the absolute nonlinear values for these films are comparable, there is a change in the sign of the absorptive nonlinearity of the films. The films developed by dip coating and pulsed laser ablation exhibit reverse saturable absorption whereas the self assembled film exhibits saturable absorption. These different nonlinear characteristics in the self assembled films can be mainly attributed to the saturation of linear absorption of the ZnO defect states.

Size-dependent enhancement of nonlinear optical properties in nanocolloids of ZnO

We have investigated the third-order nonlinearity in ZnO nanocolloids with particle sizes in the range 6-18 nm by the z-scan technique. The third-order optical susceptibility χ(3) increases with increasing particle size (R) within the range of our investigations. In the weak confinement regime, an R2 dependence of χ(3) is obtained for ZnO nanocolloids. The optical limiting response is also studied against particle size.