NIR to UV absorption spectra and the optical constants of phthalocyanines in glassy medium

Optical absorption studies of phthalocyanines (Pc-s) in borate glass matrix have been reported for the first time. Measurements have been done corresponding to photon energies between 1.1 and 6.2 eV for free base, manganese, iron, nickel, molybdenum, cobalt and copper phthalocyanines. Several new discrete transitions are observed in the UV–vis region of the spectra in addition to a strong continuum component of absorption in the IR region. Values of some of the important optical constants viz. absorption coefficient (α), molar extinction coefficient (ε), absorption cross-section (σa), band width (Δλ), electric dipole strength (q2) and oscillator strength (f) for the relevant electronic transitions are also presented. All the data reported for Pc-s in the new matrix have been compared with those corresponding to solution, vapor and thin film media.

Effect of silver nano particles on the fluorescence quantum yield of Rhodamine 6G determined using dual beam thermal lens method

Nano structured noble metals have very important applications in diverse fields as photovoltaics, catalysis, electronic and magnetic devices, etc. Here, we report the application of dual beam thermal lens technique for the determination of the effect of silver sol on the absolute fluorescence quantum yield (FQY) of the laser dye rhodamine 6G. A 532 nm radiation from a diode pumped solid state laser was used as the excitation source. It has been observed that the presence of silver sol decreases the fluorescence quantum efficiency. This is expected to have a very important consequence in enhancing Raman scattering which is an important spectrochemical tool that provides information on molecular structures. We have also observed that the presence of silver sol can enhance the thermal lens signal which makes the detection of the signal easier at any concentration.

Thermal lens technique to evaluate the fluorescence quantum yield of a schiff base

The fluorescence spectrum of the schiff base obtained from salicylaldehyde and 2-aminophenol is studied using an argon-ion laser as the excitation source and its fluorescence quantum yield (Qf) is determined using a thermal lens method. This is a nondestructive technique that gives the absolute value of Qf without the need for a fluorescence standard. The quantum-yield values are calculated for various concentrations of the solution in chloroform and also for various excitation wavelengths. The value of Qf is relatively high, and is concentration dependent. The maximum value of Qf obtained is nearly 0.78. The high value of the fluorescence quantum yield will render the schiff base useful as a fluorescent marker for biological applications. Photostability and gain studies will assess its suitability as a laser dye.

Effect of Ce3+ Ion on the X-Ray Induced Fluorescence Emission from CaS

The effect of Ce3+ on the fluorescence emission from CaS:Ce3+ phosphor is studied using X-ray excitation. Apart from the emission in the visible region, the phosphor also shows fluorescence emission in the ultraviolet region. Variation in wavelengths and intensities of these emissions due to change in dopant concentration is also analysed.

Laser induced fluorescence of BaS: Sm phosphor and energy level splitting of Sm3+ ion

Fluorescence of BaS: Sm phosphor has been studied using a pulsed Nitrogen laser (337.1 nm) as the excitation source. The spectrum consists of a broad band in the region 540–660nm superposed by the characteristic Sm3+ lines. Energy level splitting pattern of Sm3+ due to crystal field effects has been calculated and relevent field parameters are evaluated. Analysis shows that Sm3+ takes up Ba2+ substitutional sites.

Fluorescence Decay Characteristics of the Green Emission From CaF2:Ho3+

Variations in the decay times of the characteristic green emissions at 522.7, 551.3, 549.6, 547.6, 542.2, 540.2, 535.9 and 533.5nm from CaF2 :H03+ with concentration are studied at RT and LNT. A pulsed N2 laser beam of power density 1.5 MW cm-2 is used for the excitation. Temperature dependent concentration quenching of the decay times are observed for all the emission bands. But an increase in the decay time due to the reabsorption process is also observed for a few of the above bands.

Nd:Glass laser-induced damage to thin films, two-photon excited fluorescence and plasma studies

Laser-induced damage is the principal limiting constraint in the design and operation of high-power laser systems used in fusion and other high-energy laser applications. Therefore, an understanding of the mechanisms which cause the radiation damage to the components employed in building a laser and a knowledge of the damage threshold of these materials are of great importance in designing a laser system and to operate it without appreciable degradation in performance. This thesis, even though covers three distinct problems for investigations using a dye Q-switched multimode Nd:glass laser operating at 1062 nm and emitting 25 ns (FWHM) pulses, lays its main thrust on damage threshold studies on thin films. Using the same glass laser two-photon excited fluorescence in rhodamine 6G and generation and characterisation of a carbon plasma have also been carried out. The thesis is presented in seven chapters.

Nitrogen laser excited fluorescence of some rare earth doped alkaline earth fluorides

The present study is mainly concéntrated on the visible fluorescence of Ho3+ ,nd 3+ and Er 3+rare earths in alkaline earth fluoride hosts(caF2,srF2,BaF2) using a nitrogen laser excitation. A nitrogen laser was fabricated and its parametric studies were first carried out.

NIR Spectroscopic and Laser Induced Fluorescence studies of some organic molecules

Vibrational overtone spectroscopy of molecules containing X-H oscillators (X = C, N, O...) has become an effective tool for the study of molecular structure, dynamics, inter and intramolecular interactions, conformational aspects and substituent effects in aliphatic and aromatic compounds. In the present work, the author studied the NIR overtone spectra of some liquid phase organic compounds. The analysis of the CH, NH and OH overtones yielded important structural information about these systems. In an attempt to get information on electronic energy levels, we studied the pulsed Nd:YAG laser induced fluorescence spectra of certain organic compounds. The pulsed laser Raman spectra of some organic compounds are also studied. The novel high resolution technique of near infrared tunable diode laser absorption spectroscopy (TDLAS) is used to record the rotational structure of the second OH overtone spectrum of 2-propanol. The spectral features corresponding to the different molecular conformations could be identified from the high resolution spectrum. The whole work described in this thesis is divided into five chapters.

Nd:Glass Laser-Induced Damage To Thin Films, Two-Photon Excited Fluorescence And Plasma Studies

Laser-induced damage is the principal limiting constraint in the design and operation of high-power laser systems used in fusion and other high-energy laser applications. Therefore, an understanding of the mechanisms which cause the radiation damage to the components employed in building a laser and a knowledge of the damage threshold of these materials are of great importance in designing a laser system and to operate it without appreciable degradation in performance. This thesis, even though covers three distinct problems for investigations using a dye Q-switched multimode Nd:glass laser operating at 1062 nm and emitting 25 ns (FWHM) pulses, lays its main thrust on damage threshold studies on thin films. Using the same glass laser two-photon excited fluorescence in rhodamine 6G and generation and characterisation of a carbon plasma have also been carried out.

“Investigations on Vibrational Overtones in the NIR region and Laser Induced Fluorescence in some selected compounds”

The central theme of this research concerns the study of vibrationally excited molecules. We have used the local mode description of such vibrational states, and this -model has now gained general acceptance. A central feature of the model is the Wloealizafion of vibrational energy. A study of these high—energy localized states provides example, becauseof this localization, overtone spectra, which measure the absorption of T vibrational energy, are extremely sensitive to the properties of X-H bonds. We also use -overtone spectra to study the conformation of molecules, i.e., the relative internal orientation of their bonds. The thesis comprises six chapters

Enhanced UV emission from ZnO nanoflowers synthesized by the hydrothermal process

ZnO nanoflowers were synthesized by the hydrothermal process at an optimized growth temperature of 200 ◦C and a growth/reaction time of 3 h. As-prepared ZnO nanoflowers were characterized by x-ray diffraction, scanning electron microscopy, UV–visible and Raman spectroscopy. X-ray diffraction and Raman studies reveal that the as-synthesized flower-like ZnO nanostructures are highly crystalline with a hexagonal wurtzite phase preferentially oriented along the (1 0 1 1) plane. The average length (234–347 nm) and diameter (77–106 nm) of the nanorods constituting the flower-like structure are estimated using scanning electron microscopy studies. The band gap of ZnO nanoflowers is estimated as 3.23 eV, the lowering of band gap is attributed to the flower-like surface morphology and microstructure of ZnO. Room temperature photoluminescence spectrum shows a strong UV emission peak at 392 nm, with a suppressed visible emission related to the defect states, indicating the defect free formation of ZnO nanoflowers that can be potentially used for UV light-emitting devices. The suppressed Raman bands at 541 and 583 cm−1 related to defect states in ZnO confirms that the ZnO nanoflowers here obtained have a reduced presence of defects

Boosted UV emission at 349 nm from mesoporous ZnS

Relatively oxygen-free mesoporous cubic ZnS particles were synthesised via a facile solvo-hydrothermal route using a water–acetonitrile combination. Boosted UV emission at 349 nm is observed from the ZnS prepared by the solvo-hydrothermal route. The increased intensity of this UV emission is attributed to activation of whispering gallery modes of almost elliptical microstructures made of porous nanostructures.

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.

Novel Electrochemical and Fluorescence Sensors for Food Additives and Neurotransmitters

There is an enormous demand for chemical sensors in many areas and disciplines including chemistry, biology, clinical analysis, environmental science. Chemical sensing refers to the continuous monitoring of the presence of chemical species and is a rapidly developing field of science and technology. They are analytical devices which transform chemical information generating from a reaction of the analyte into an measurable signal. Due to their high selectivity, sensitivity, fast response and low cost, electrochemical and fluorescent sensors have attracted great interest among the researchers in various fields. Development of four electrochemical sensors and three fluorescent sensors for food additives and neurotransmitters are presented in the thesis. Based on the excellent properties of multi walled carbon nanotube (MWCNT), poly (L-cysteine) and gold nanoparticles (AuNP) four voltammetric sensors were developed for various food additives like propyl gallate, allura red and sunset yellow. Nanosized fluorescent probes including gold nanoclusters (AuNCs) and CdS quantum dots (QDs) were used for the fluorescent sensing of butylated hydroxyanisole, dopamine and norepinephrine. A total of seven sensors including four electrochemical sensors and three fluorescence sensors have been developed for food additives and neurotransmitters.