High-Spin and Emissive Molecular Materials: Synthesis and Characterization of New Polynuclear Ni(II) Complexes from the Use of Aromatic Schiff Bases as Bridging Ligands

The employment of the bridging/chelating Schiff bases, N-salicylidene-4-methyl-o-aminophenol (samphH2) and N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH2), in nickel cluster chemistry has afforded eight polynuclear Ni(II) complexes with new structural motifs, interesting magnetic and optical properties, and unexpected organic ligand transformations. In the present thesis, Chapter 1 deals with all the fundamental aspects of polynuclear metal complexes, molecular magnetism and optics, while research results are reported in Chapters 2 and 3. In the first project (Chapter 2), I investigated the coordination chemistry of the organic chelating/bridging ligand, N-salicylidene-4-methyl-o-aminophenol (samphH2). The general NiII/tBuCO2-/samphH2 reaction system afforded two new tetranuclear NiII clusters, namely [Ni4(samph)4(EtOH)4] (1) and [Ni4(samph)4(DMF)2] (2), with different structural motifs. Complex 1 possessed a cubane core while in complex 2 the four NiII ions were located at the four vertices of a defective dicubane. The nature of the organic solvent was found to be of pivotal importance, leading to compounds with the same nuclearity, but different structural topologies and magnetic properties. The second project, the results of which are summarized in Chapter 3, included the systematic study of a new optically-active Schiff base ligand, N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH2), in NiII cluster chemistry. Various reactions between NiX2 (X- = inorganic anions) and nacbH2 were performed under basic conditions to yield six new polynuclear NiII complexes, namely (NHEt3)[Ni12(nacb)12(H2O)4](ClO4) (3), (NHEt3)2[Ni5(nacb)4(L)(LH)2(MeOH)] (4), [Ni5(OH)2(nacb)4(DMF)4] (5), [Ni5(OMe)Cl(nacb)4(MeOH)3(MeCN)] (6), (NHEt3)2[Ni6(OH)2(nacb)6(H2O)4] (7), and [Ni6(nacb)6(H2O)3(MeOH)6] (8). The nature of the solvent, the inorganic anion, X-, and the organic base were all found to be of critical importance, leading to products with different structural topologies and nuclearities (i.e., {Ni5}, {Ni6} and {Ni12}). Magnetic studies on all synthesized complexes revealed an overall ferromagnetic behavior for complexes 4 and 8, with the remaining complexes being dominated by antiferromagnetic exchange interactions. In order to assess the optical efficiency of the organic ligand when bound to the metal centers, photoluminescence studies were performed on all synthesized compounds. Complexes 4 and 5 show strong emission in the visible region of the electromagnetic spectrum. Finally, the ligand nacbH2 allowed for some unexpected organic transformations to occur; for instance, the pentanuclear compound 5 comprises both nacb2- groups and a new organic chelate, namely the anion of 5-chloro-2-[(3-hydroxy-4-oxo-1,4-dihydronaphthalen-1-yl)amino]benzoic acid. In the last section of this thesis, an attempt to compare the NiII cluster chemistry of the N-naphthalidene-2-amino-5-chlorobenzoic acid ligand with that of the structurally similar but less bulky, N-salicylidene-2-amino-5-chlorobenzoic acid (sacbH2), was made.

Optical and electrical properties of amorphous zinc tin oxide thin films examined for thin film transistor application

Structural, electronic, and optical properties of amorphous and transparent zinc tin oxide films deposited on glass substrates by pulsed laser deposition (PLD) were examined for two chemical compositions of Zn:Sn=1:1 and 2:1 as a function of oxygen partial pressure PO2 used for the film deposition and annealing temperature. Different from a previous report on sputter-deposited films Chiang et al., Appl. Phys. Lett. 86, 013503 2005 , the PLD-deposited films crystallized at a lower temperature 450 °C to give crystalline ZnO and SnO2 phases. The optical band gaps Tauc gaps were 2.80−2.85 eV and almost independent of oxygen PO2 , which are smaller than those of the corresponding crystals 3.35−3.89 eV . Films deposited at low PO2 showed significant subgap absorptions, which were reduced by postthermal annealing. Hall mobility showed steep increases when carrier concentration exceeded threshold values and the threshold value depended on the film chemical composition. The films deposited at low PO2 2 Pa had low carrier concentrations. It is thought that the low PO2 produced high-density oxygen deficiencies and generated electrons, but these electrons were trapped in localized states, which would be observed as the subgap absorptions. Similar effects were observed for 600 °C crystallized films and their resistivities were increased by formation of subgap states due to the reducing high-temperature condition. High carrier concentrations and large mobilities were obtained in an intermediate PO2 region for the as-deposited films.

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.

Lithium Containing Complex Metal Oxides and Metal phosphates:Investigations on their synthesis and various characterizations for rechargeable lithium battery applications

The work presented in the thesis is centered around two important types of cathode materials, the spinel structured LixMn204 (x =0.8to1.2) and the phospho -oIivine structured LiMP04 (M=Fe and Ni). The spinel system LixMn204, especially LiMn204 corresponding to x= 1 has been extensively investigated to understand its structural electrical and electrochemical properties and to analyse its suitability as a cathode material in rechargeable lithium batteries. However there is no reported work on the thermal and optical properties of this important cathode material. Thermal diffusivity is an important parameter as far as the operation of a rechargeable battery is concerned. In LixMn204, the electronic structure and phenomenon of Jahn-Teller distortion have already been established theoretically and experimentally. Part of the present work is an attempt to use the non-destructive technique (NDT) of photoacoustic spectroscopy to investigate the nature of the various electronic transitions and to unravel the mechanisms leading to the phenomenon of J.T distortion in LixMn204.The phospho-olivines LiMP04 (M=Fe, Ni, Mn, Co etc) are the newly identified, prospective cathode materials offering extremely high stability, quite high theoretical specific capacity, very good cycIability and long life. Inspite of all these advantages, most of the phospho - olivines especially LiFeP04 and LiNiP04 show poor electronic conductivity compared to LixMn204, leading to low rate capacity and energy density. In the present work attempts have been made to improve the electronic conductivity of LiFeP04 and LiNiP04 by adding different weight percentage MWNT .It is expected that the addition of MWNT will enhance the electronic conductivity of LiFeP04 and LiNiP04 with out causing any significant structural distortions, which is important in the working of the lithium ion battery.

Nonlinear optical characteristics of nanocomposites of ZnO–TiO2–SiO2

In this article we present the nonlinear optical properties of ZnO–TiO2–SiO2 nanocomposites prepared by colloidal chemical synthesis. Nonlinear optical response of these samples is studied using nanosecond laser pulses at an off-resonance wavelength. The nonlinearity of the silica colloid is low and its nonlinear response can be improved by making composites with ZnO and TiO2. These nanocomposites show self-defocusing nonlinearity and good nonlinear absorption behaviour. The nonlinear refractive index and the nonlinear absorption increases with increasing ZnO volume fraction. The observed nonlinear absorption is explained by two photon absorption followed by weak free carrier absorption and nonlinear scattering. ZnO–TiO2–SiO2 is a potential nanocomposite material for the development of nonlinear optical devices with a relatively small limiting threshold.

Spectral and nonlinear optical characteristics of nanocomposites of ZnO–Ag

In this Letter we present the spectral and nonlinear optical properties of ZnO–Ag nanocomposites prepared by colloidal chemical synthesis. Obvious enhancement of ultraviolet (UV) emission of the samples is observed and the strongest UV emission is over three times than that of pure ZnO. These nanocomposites show self-defocusing nonlinearity and good nonlinear absorption behaviour which increases with increasing Ag volume fraction. The observed nonlinear absorption is explained through two photon absorption followed by free carrier absorption. ZnO–Ag is a potential nanocomposite material for the UV light emission and for the development of nonlinear optical devices with a relatively small limiting threshold.

Linear and nonlinear optical characteristics of ZnO-SiO2 nanocomposites.

We present the spectral and nonlinear optical properties of ZnO-SiO2 nanocomposites prepared by colloidal chemical synthesis. Obvious enhancement of ultraviolet (UV) emission of the samples is observed, and the strongest UV emission of a typical ZnO-SiO2 nanocomposite is over three times stronger than that of pure ZnO. The nonlinearity of the silica colloid is low, and its nonlinear response can be improved by making composites with ZnO. These nanocomposites show self-defocusing nonlinearity and good nonlinear absorption behavior. The observed nonlinear absorption is explained through two photon absorption followed by weak free carrier absorption and nonlinear scattering. The nonlinear refractive index and the nonlinear absorption increase with increasing ZnO volume fraction and can be attributed to the enhancement of exciton oscillator strength. ZnO-SiO2 is a potential nanocomposite material for the UV light emission and for the development of nonlinear optical devices with a relatively small limiting threshold.

Enhanced shape anisotropy and magneto-optical birefringence by high energy ball milling in NixFe1−xFe2O4 ferrofluids

Ferrofluids belonging to the series NixFe1 xFe2O4 were synthesised by two different procedures—one by standard co-precipitation techniques, the other by co-precipitation for synthesis of particles and dispersion aided by high-energy ball milling with a view to understand the effect of strain and size anisotropy on the magneto-optical properties of ferrofluids. The birefringence measurements were carried out using a standard ellipsometer. The birefringence signal obtained for chemically synthesised samples was satisfactorily fitted to the standard second Langevin function. The ball-milled ferrofluids showed a deviation and their birefringence was enhanced by an order. This large enhancement in the birefringence value cannot be attributed to the increase in grain size of the samples, considering that the grain sizes of sample synthesised by both modes are comparable; instead, it can be attributed to the lattice strain-induced shape anisotropy(oblation) arising from the high-energy ball-milling process. Thus magnetic-optical (MO) signals can be tuned by ball-milling process, which can find potential applications.

Investigations on Magnetic, Optical and Transport Properties of Magnetic Nanofluids for Engineering and Biomedical Applications

Department of Physics, Cochin University of Science & Technology

Photoacoustic investigation of the optical and thermal properties of selected amorphous chalcogenide semiconductors

This thesis work has mainly concentrated on the investigation of the ,optical and thermal properties of binary semiconducting chalcogenide glasses belonging to the AivB¥5x and AZBXEX families. The technique used for these studies is a relatively new one namely, the photoacoustic (PA) technique. This technique is based on the detection of acoustic signal produced in an enclosed volume when the sample is irradiated by an intensity modulated radiation. The signal produced depends upon the optical properties of the sample, and the thermal properties of the sample, backing material and the surrounding gas. For the present studies an efficient signal beam gas-microphone PA spectrometer, consisting of a high power Xenon lamp, monochromator, light beam chopper, PA cell with microphone and lock-in amplifier, has been set up. Two PA cells have been fabricated: one for room temperature measurements and another for measurements at high temperatures. With the high temperature PA cell measurements can be taken upto 250°C. Provisions are incorporated. in both the cells to change the volume and to use different backing materials for the sample. The cells have been calibrated by measuring the frequency response of the cells using carbon black as the sample

Synthesis and characterization of Tellurium oxide glasses for photonic applications

Tellurite glasses are photonic materials of special interest to the branch of optoelectronic and communication, due to its important optical properties such as high refractive index, broad IR transmittance, low phonon energy etc. Tellurite glasses are solutions to the search of potential candidates for nonlinear optical devices. Low phonon energy makes it an efficient host for dopant ions like rare earths, allowing a better environment for radiative transitions. The dopant ions maintain majority of their individual properties in the glass matrix. Tellurites are less toxic than chalcogenides, more chemically and thermally stable which makes them a highly suitable fiber material for nonlinear applications in the midinfrared and they are of increased research interest in applications like laser, amplifier, sensor etc. Low melting point and glass transition temperature helps tellurite glass preparation easier than other glass families. In order to probe into the versatility of tellurite glasses in optoelectronic industry; we have synthesized and undertaken various optical studies on tellurite glasses. We have proved that the highly nonlinear tellurite glasses are suitable candidates in optical limiting, with comparatively lower optical limiting threshold. Tuning the optical properties of glasses is an important factor in the optoelectronic research. We have found that thermal poling is an efficient mechanism in tuning the optical properties of these materials. Another important nonlinear phenomenon found in zinc tellurite glasses is their ability to switch from reverse saturable absorption to saturable absorption in the presence of lanthanide ions. The proposed thesis to be submitted will have seven chapters

Electro-Optical Studies On Metal Phthalocyanines

Metal phthalocyanines have some unique optical properties which are exploited for dyeing fibers and films used in applicationslike dye lasing and optical information storage. Aggregation of dye molecules modifies their absorption and emission spectra with concomitant degradation in their energy transfer characteristics. MPcs as such have poor processability and are seldom used in solid matrices. The finest energy transfer characteristics are shown by the monomers of metal phthalocyanines. In the third chapter of this thesis the studies on two series of metal phthalocyanines are repoted

An Optical limiter based on Ferrofluids

We report an optical limiter based on ferrofluids which has a very high shelf life and remarkable thermal stability, which are important requirements for sustainable use with intense lasers. The colloidal suspensions contain nanosized particles of approximately 80 Å diameter, with a number density of the order of 1022 /m3. The nonlinear optical transmission of the samples is studied using nanosecond and femtosecond laser pulses. Excited state absorption phenomena contribute to enhanced limiting in the nanosecond excitation regime. An advantageous feature of ferrofluids in terms of device applications is that their optical properties are controllable by an external magnetic field.