Realization of a Scanning Photoacoustic Technique: Thermal properties of Bulk and Film Samples

Among the large number of photothcrmal techniques available, photoacoustics assumes a very significant place because of its essential simplicity and the variety of applications it finds in science and technology. The photoacoustic (PA) effect is the generation of an acoustic signal when a sample, kept inside an enclosed volume, is irradiated by an intensity modulated beam of radiation. The radiation absorbed by the sample is converted into thermal waves by nonradiative de-excitation processes. The propagating thermal waves cause a corresponding expansion and contraction of the gas medium surrounding the sample, which in tum can be detected as sound waves by a sensitive microphone. These sound waves have the same frequency as the initial modulation frequency of light. Lock-in detection method enables one to have a sufficiently high signal to noise ratio for the detected signal. The PA signal amplitude depends on the optical absorption coefficient of the sample and its thermal properties. The PA signal phase is a function of the thermal diffusivity of the sample.Measurement of the PA amplitude and phase enables one to get valuable information about the thermal and optical properties of the sample. Since the PA signal depends on the optical and thennal properties of the sample, their variation will get reflected in the PA signal. Therefore, if the PA signal is collected from various points on a sample surface it will give a profile of the variations in the optical/thennal properties across the sample surface. Since the optical and thermal properties are affected by the presence of defects, interfaces, change of material etc. these will get reflected in the PA signal. By varying the modulation frequency, we can get information about the subsurface features also. This is the basic principle of PA imaging or PA depth profiling. It is a quickly expanding field with potential applications in thin film technology, chemical engineering, biology, medical diagnosis etc. Since it is a non-destructive method, PA imaging has added advantages over some of the other imaging techniques. A major part of the work presented in this thesis is concemed with the development of a PA imaging setup that can be used to detect the presence of surface and subsmface defects in solid samples.Determination of thermal transport properties such as thermal diffusivity, effusivity, conductivity and heat capacity of materials is another application of photothennal effect. There are various methods, depending on the nature of the sample, to determine these properties. However, there are only a few methods developed to determine all these properties simultaneously. Even though a few techniques to determine the above thermal properties individually for a coating can be found in literature, no technique is available for the simultaneous measurement of these parameters for a coating. We have developed a scanning photoacoustic technique that can be used to determine all the above thermal transport properties simultaneously in the case of opaque coatings such as paints. Another work that we have presented in this thesis is the determination of thermal effusivity of many bulk solids by a scanning photoacoustic technique. This is one of the very few methods developed to determine thermal effiisivity directly.

Studies on optical attenuation in sea water using dye laser and laser propagation in a turbulent medium

The central theme of the work presented in this thesis is a careful investigation of the factors influencing the attenuation of laser beam through sea water. The thesis presents a detailed report of the work done by the author on the attenuation studies in sea water and on laser propagation through a turbulent medium. The thesis contains six chapters which are more or less self-contained with separate abstracts and references. The first chapter is divided into two parts. The first part introduces the subject of laser propagation through sea water. It includes a brief description of optical properties of sea water followed by a review of the earlier works on attenuation studies in water. The second part gives the theoretical background of the problem of laser propagation through a turbulent medium.

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

Investigations On The Preparation And Properties Of Reactively Evaporated Lead Sulphide And Tin Telluride Thin Films

The work reported in this thesis is the preparation, and the structural, electrical and optical properties of reactively evaporated lead sulphide and tin telluride thin films. The three temperature method had been used for the preparation of these semiconductor thin films. In this preparation technique constituent elements are evaporated from separate sources with the substrate kept at a particular temperature. when one of the constituent element is a gas near room temperature, the method is often called reactive evaporation. It has been found for many materials that a stoichiometric interval exists with a limited range of flux and substrate temperature. Usually this technique is used for the preparation of thin films of high melting point compounds or of materials which decompose during evaporation. Tin telluride and lead sulphide are neither high melting point materials nor do they decompose on melting. But even than reactive evaporation offers the possibility of changing the ratios of the flux of the constituent elements within a wide range and studying its effect on the properties of the films

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.

On the synthesis and magnetic properties of multiwall carbon nanotube– superparamagnetic iron oxide nanoparticle nanocomposites

Multiwall carbon nanotubes (MWCNTs) possessing an average inner diameter of 150 nm were synthesized by template assisted chemical vapor deposition over an alumina template. Aqueous ferrofluid based on superparamagnetic iron oxide nanoparticles (SPIONs) was prepared by a controlled co-precipitation technique, and this ferrofluid was used to fill the MWCNTs by nanocapillarity. The filling of nanotubes with iron oxide nanoparticles was confirmed by electron microscopy. Selected area electron diffraction indicated the presence of iron oxide and graphitic carbon from MWCNTs. The magnetic phase transition during cooling of the MWCNT–SPION composite was investigated by low temperature magnetization studies and zero field cooled (ZFC) and field cooled experiments. The ZFC curve exhibited a blocking at ∼110 K. A peculiar ferromagnetic ordering exhibited by the MWCNT–SPION composite above room temperature is because of the ferromagnetic interaction emanating from the clustering of superparamagnetic particles in the constrained volume of an MWCNT. This kind of MWCNT–SPION composite can be envisaged as a good agent for various biomedical applications

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

Evaluation Of A Novel Method Of Real Time Computer Assisted Spine Surgery

In this paper the effectiveness of a novel method of computer assisted pedicle screw insertion was studied using testing of hypothesis procedure with a sample size of 48. Pattern recognition based on geometric features of markers on the drill has been performed on real time optical video obtained from orthogonally placed CCD cameras. The study reveals the exactness of the calculated position of the drill using navigation based on CT image of the vertebra and real time optical video of the drill. The significance value is 0.424 at 95% confidence level which indicates good precision with a standard mean error of only 0.00724. The virtual vision method is less hazardous to both patient and the surgeon

Synthesis and characterization of 3d-transition metals doped ZnO thin films and nanostructures for possible spintronic applications

The objective of the present study is the formation of single phase Zn1−xTMxO thin films by PLD and increase the solubility limit of TM dopants. The TM doped ZnO nanostructures were also grown by hydrothermal method. The structural and morphological variation of ZnO:TM thin films and nanostructures with TM doping concentration is also investigated. The origin and enhancement of ferromagnetism in single phase Zn1−xTMxO thin films and nanostructures using spectroscopic techniques were also studied. The dependence of ablation parameters on the structural and optical properties of ZnO thin films were studied

Investigation on the panchromaticity of silver-doped poly(vinyl alcohol)/acrylamide photopolymer

An investigation on the panchromaticity of a silver-doped poly(vinyl alcohol)/acrylamide photopolymer system is presented in this paper. Frequency-doubled Nd:YAG (532 nm) and Arþ (488 nm) lasers were used for the characterization of the films. Previous studies using an He–Ne laser (632:8 nm) showed that plane-wave transmission grating with a high diffraction efficiency of 75% could be stored in the optimized film. From the present study, it was noted that transmission gratings with 70% diffraction efficiency could be recorded using Arþ and Nd:YAG lasers, thereby elucidating the possibility of using the developed photopolymer system as a competent panchromatic recording medium

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.