Studies on Chemical Bath Deposited Semiconducting Copper Selenide and Iron Sulfide Thin Films Useful For Photovoltaic Applications

Chemical bath deposition (CBD)is one of the simplest, very convient and probably the cheapest method for thin film preparation. Photovoltaic is the cleanest and the most efficient mode of conversion of energy to electrical power. Silicon is the most popular material in this field. The present study on chemical bath deposited semiconducting copper selenide and iron sulfide thin films useful for photovoltaic applications. Semiconducting thin films prepared by chemical deposition find applications as photo detectors, solar control coatings and solar cells. Copper selenide is a p-type semiconductor that finds application in photovolitics. Several heterojunction systems such as Cu2-xSe/ZnSe (for injection electro luminescence), Cu2Se/AgInSe2 and Cu2Se/Si (for photodiodes), Cu2-xSe/CdS, Cu2-xSe/CdSe, CuxSe/InP and Cu2-xSe/Si for solar cells are reported. A maximum efficiency of 8.3% was achieved for the Cu2-xSe/Si cell, various preparation techniques are used for copper selenide like vacuum evaporation, direct reaction, electrodeposition and CBD. Instability of the as-prepared films was investigation and is accounted as mainly due to deviation from stoichiometry and the formation of iron oxide impurity. A sulphur annealing chamber was designed and fabricated for this work. These samples wee also analysed using optical absorption technique, XPS (X-ray Photoelectron Spectroscopy) and XRD.(X-Ray Diffraction).The pyrite films obtained by CBD technique showed amorphous nature and the electrical studies carried out showed the films to be of high resistive nature. Future work possible in the material of iron pyrite includes sulphur annealing of the non-stochiometric iron pyrite CBD thin films in the absence of atmospheric oxygen

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.

Optical and Thermal Characterization of Dye Intercalated Montmorillonites and Rare Earth Doped Materials

Nondestructive photothermal methods as well as optical absorption and fluorescence spectroscopy are utilized to characterise three different materials, both thermally and optically. The possibility of using montmorillonite clay minerals, after textile waste-water treatment, is investigated for further applications. The laser induced luminescence studies and thermal characterisation of certain rare earth titanates prepared by self propagating high temperature synthesis method are also presented. Moreover, effort is made to characterise rare earth doped sol gel silica glasses with the help of these nondestructive techniques.

ANALYSIS, MODIFICATION, AND EVALUATION OF THE COLD FLOW PROPERTIES OF VEGETABLE OILS AS BASE OIL FOR INDUSTRIAL LUBRICANTS

Poor cold flow properties of vegetable oils are a major problem preventing the usage of many abundantly available vegetable oils as base stocks for industrial lubricants. The major objective of this research is to improve the cold flow properties of vegetable oils by various techniques like additive addition and different chemical modification processes. Conventional procedure for determining pour point is ASTM D97 method. ASTM D97 method is time consuming and reproducibility of pour point temperatures is poor between laboratories. Differential Scanning Calorimetry (DSC) is a fast, accurate and reproducible method to analyze the thermal activities during cooling/heating of oil. In this work coconut oil has been chosen as representative vegetable oil for the analysis and improvement cold flow properties since it is abundantly available in the tropics and has a very high pour point of 24 °C. DSC is used for the analysis of unmodified and modified vegetable oil. The modified oils (with acceptable pour points) were then subjected to different tests for the valuation of important lubricant properties such as viscometric, tribological (friction and wear properties), oxidative and corrosion properties.A commercial polymethacrylate based PPD was added in different percentages and the pour points were determined in each case. Styrenated phenol(SP) was added in different concentration to coconut oil and each solution was subjected to ASTM D97 test and analysis by DSC. Refined coconut oil and other oils like castor oil, sunflower oil and keranja oil were mixed in different proportions and interesterification procedure was carried out. Interesterification of coconut oil with other vegetable oils was not found to be effective in lowering the pour point of coconut oil as the reduction attained was only to the extent of 2 to 3 °C.Chemical modification by acid catalysed condensation reaction with coconut oil castor oil mixture resulted in significant reduction of pour point (from 24 ºC to -3 ºC). Instead of using triacylglycerols, when their fatty acid derivatives (lauric acid- the major fatty acid content of coconut oil and oleic acid- the major fatty acid constituents of monoand poly- unsaturated vegetable oils like olive oil, sunflower oil etc.) were used for the synthesis , the pour point could be brought down to -42 ºC. FTIR and NMR spectroscopy confirmed the ester structure of the product which is fundamental to the biodegradability of vegetable oils. The tribological performance of the synthesised product with a suitable AW/EP additive was comparable to the commercial SAE20W30 oil. The viscometric properties (viscosity and viscosity index) were also (with out additives) comparable to commercial lubricants. The TGA experiment confirmed the better oxidative performance of the product compared to vegetable oils. The sample passed corrosion test as per ASTM D130 method.

Modification of Polypropylene/Glass Fiber Composites with Nanosilica

Poly(propylene) (PP) reinforced with short glass fiber was modified with precipitated nanosilica (pnS) by melt mixing. The weight of the glass fiber was varied by keeping the pnS at optimum level. The properties of the composites were studied using universal testing machine, dynamic mechanic analyser (DMA), differential Scanning calorimetry (DSC) and thermo gravimetric analyser (TGA). The amount of the glass fiber required for a particular modulus could be reduced by the addition of nanosilica.

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.

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.

Synthesis and Characterisation of Thermoplastic Ionomers based on Natural Rubber

Chemically modified novel thermo-reversible zinc sulphonated ionomers based on natural rubber (NR), radiation induced styrene grafted natural rubber (RI-SGNR), and chemically induced styrene grafted natural rubber (CI-SGNR) were synthesized using acetyl sulphate/zinc acetate reagent system. Evidence for the attachment of sulphonate groups has been furnished by FTIR spectra. which was supplanted by FTNMR results. Estimation of the zinc sulphonate group was done using spectroscopic techniques such as XRFS and ICPAES. The TGA results prove improvement in the therrno-oxidative stability of the modified natural rubber. Both DSC and DMTA studies show that the incorporation of the ionic groups affect the thermal transition of the base polymer. Retention of the improved physical properties of the novel ionomers even after three repeated cycles of mastication and molding at 120 degree C may be considered as the evidence for the reprocessabiJity of the ionomer. Effect of both particulate (carbon black. silica & zinc stearate) and fibrous fillers (nylon & glass) on the properties of the radiation induced styrene grafted natural rubber ionomer has been evaluated. Incorporation of HAF carbon black results in maximum improvement in physical properties. Silica reinforces the backbone chain and weakens the ionic associations. Zinc stearate plays the dual role of reinforcement and ptasticization. The nylon and glass filled lonorner compounds show good improvement in the physical properties in comparison with the neat ionomer. Dispersion and adhesion of the fillers in the ionomer matrix has been amply supported by their SEM micrographs. Microwave probing of the electrical behavior of the 26.5 ZnSRISGNR ionomer reveals that the maximum relative complex conductivity and the complex permittivity appear at the frequency of 2.6 GHz. The complex conductivity of the base polymer increases from 1.8x 10.12 S/cm to 3.3xlO·4 S/cm. Influence of fillers on the dielectric constant and conductivity of the new ionic thermoplastic elastomer has been studied. The ionomer I nylon compound shows the highest microwave conductivity. Use of the 26.5 ZnS-RISGNR ionomer as a compatibilizer for obtaining the technologically compatible blends from the immiscible SBR/NBR system has been verified. The heat fugitive ionic cross-linked natural rubber may be, therefore, useful as an alternative to vulcanized rubber and thermoplastic elastomer

Laser Induced Photothermal Investigations on Thermal and Transport Properties of Certain Selected Photonic Materials

Discovery of coherent optical sources four decades ago has revolutionized all fields of scientific development. One of the path breaking applications of lasers is the emergence of various thermo optic techniques to unravel some of the mysteries of light matter interactions.Thermo optic technique is a valuable tool to evaluate optical and thermal properties of materials in solid,liquid and gaseous states .This technique can also be employed effectively in nondestructive quality evaluation. In this doctoral thesis , the use of photothermal techniques based on photoacoustic and photothermal deflection phenomena for the study of certain class of photonics materials such as semiconductors, nano metal dispersed ceramics, composites of conducting polymers and liquid crystals is elaborated.

Characterization of Photonic Materials Using Thermal Lens Technique

The subject of Photonics is concerned with the generation,control and utilization of photons for performing a variety of tasks.It came to existence as a consequence of the harmonious fusion of optical methods with electronic technology.Wide spread use of laser based methods in electronics is slowly replacing elecrtons with photons in the field of Communication,Control and Computing .Therefore,there is a need to promote the R & D activities in the area of Photonics and to generate well trained manpower in laser related fields.Development and characterization of photonic materials is an important subject of research in the field of Photonics.Optical and thermal characterization of photonic materials using thermal lens technique is a PhD thesis in the field of Photonics in which the author describes how thermal lens effect can be used to characterize themal and optical properties of photonic materials.Plausibility of thermal lens based logic gates is also presented in this thesis.

Optical limiting and thermal lensing studies in C60

Optical limiting and thermo-optic properties of C60 in toluene are studied using 532 nm, 9 ns pulses from a frequency-doubled Nd:YAG laser. Optical limiting studies in these fullerene molecules lead to the conclusion that reverse saturable absorption is the major mechanism for limiting properties in these molecules. Thermal lensing measurements are also performed in fullerene solutions. The quadratic dependence of thermal lens signal on incident energy confirms that enhanced optical absorption by the sample via excited triplet state absorption may play a leading role in the limiting property.

Photoluminescence studies on rare earth titanates prepared by self-propagating high temperature synthesis method

The laser-induced luminescence studies of the rare earth titanates (R2Ti2O7) (R = La, Nd and Gd) using 355 nm radiation from an Nd:YAG laser are presented. These samples with submicron or nanometer size are prepared by the self-propagating high temperature synthesis (SHS) method and there is no known fluorescence shown by these rare earths in the visible region. Hence, the luminescence transitions shown by the La2Ti2O7 near 610 nm and Gd2Ti2O7 near 767 nm are quite interesting. Though La3+ ions with no 4f electrons have no electronic energy levels that can induce excitation and luminescence processes in the visible region, the presence of the Ti3+ ions leads to luminescence in this region.

Size dependent fluorescence spectroscopy of nanocolloids of ZnO

In this article we present size dependent spectroscopic observations of nanocolloids of ZnO. ZnO is reported to show two emission bands, an ultraviolet (UV) emission band and another in the green region. Apart from the known band gap 380 nm and impurity 530 nm emissions, we have found some peculiar features in the fluorescence spectra that are consistent with the nanoparticle size distribution. Results show that additional emissions at 420 and 490 nm are developed with particle size. The origin of the visible band emission is discussed. The mechanism of the luminescence suggests that UV luminescence of ZnO colloid is related to the transition from conduction band edge to valence band, and visible luminescence is caused by the transition from deep donor level to valence band due to oxygen vacancies and by the transition from conduction band to deep acceptor level due to impurities and defect states. A correlation analysis between the particle size and spectroscopic observations is also discussed.

Excitation and Emission Characteristics of Pretreated SrS:Mn:Ce Phosphors

Excitation and emission spectra of SrS : Mn : Ce phosphors have been studied in detail at various Mn and Ce concentrations. In order to study the effect of external pressure on phosphors, the samples were pretreated under various pressures. Four bands around 470 nm, 530 nm, 310 nm and 620 nm were observed, when the samples were excited with 265 nm radiation. The effect of pressure is to reduce the fluorescence ability of the phosphors, and the luminescence vanishes above O· 1 ton m-2 pressure. The fluorescence ability, however, can be regained on retiring the sample. The emission mechanism has been attributed to two luminescentcenters in the forbidden gap. An appreciable amount of photocurrent has also been observed for the sample.