Zeolite Encapsulated Complexes Of Fe,Co,Ni,Cu And Pd:Synthesis , Characterization And Catalysis-2003

This thesis deals with the synthesis, characterization and catalysis activity studies of some zeolite encapsulated complexes. Encapsulation inside the zeolite cages makes the catalysts more stable. Further, the framework prevents the complexes from dimerising. Catalysis by metal complexes encapsulated in the cavities of zeolites and other molecular sieves has many features of homogeneous, heterogenous and enzymatic catalysis. Serious attempts has been made to gain product selectivity in catalysis .The catalytic activity shown by the encapsulated complexes can be correlated to the structure of the active site inside the zeolite pore. It deals with the studies on the partial oxidation of benzyl alcohol to benzaldehyde. The oxidatio was carried out using hydrogen peroxide as oxidant in presence of PdYDMG and CuYSPP as catalysts. The product (benzaldehyde) was detected using TLC and confirmed using GC.The catalytic activity of the complexes was tested for oxidation under various conditions. The operating conditions like the amount of the catalyst, reaction time, oxidant to substrate ratio, reaction temprature, and solvents have been optimized. No further oxidation products were obtained on continuing the reaction for four hours beyond the optimum time. Maximum conversion was obtained at room temperature and the percentage conversion decreased with increase in temperature. Activity was found to be dependent on the solvent used. With increasing awareness about the dangers of environmental degradation, research in chemistry is getting increasing geared to the development of “green chemistry,” by designing environmentally friendly products and processes that bring down the generation and use of hazardous substances.

Removal of Fe(III) using a polystyrene anchored Schiff base

Salicylaldehyde Schiff base of amino-methylated polystyrene has been developed as a novel reagent for the removal of Fe(III) from solutions. The selectivity of the metal ion uptake over a wide range of different concentrations of metal ion, effect of pH, ligand concentration and the influence of other foreign ions were studied. A very good selectivity was achieved for the removal of the ion. It was found that 0.01 g of the ligand was sufficient to achieve about 96% removal of the metal ion in terms of concentration (ppm) from a 30 ppm solution in acidic pH.

Spray Pyrolysed Zinc Oxide Thin Films : Effects of Doping and Ion Beam Irradiation

In recent years scientists have made rapid and significant advances in the field of semiconductor physics. One of the most important fields of current interest in materials science is the fundamental aspects and applications of conducting transparent oxide thin films (TCO). The characteristic properties of such coatings are low electrical resistivity and high transparency in the visible region. The first semitransparent and electrically conducting CdO film was reported as early as in 1907 [1]. Though early work on these films was performed out of purely scientific interest, substantial technological advances in such films were made after 1940. The technological interest in the study of transparent semiconducting films was generated mainly due to the potential applications of these materials both in industry and research. Such films demonstrated their utility as transparent electrical heaters for windscreens in the aircraft industry. However, during the last decade, these conducting transparent films have been widely used in a variety of other applications such as gas sensors [2], solar cells [3], heat reflectors [4], light emitting devices [5] and laser damage resistant coatings in high power laser technology [6]. Just a few materials dominate the current TCO industry and the two dominant markets for TCO’s are in architectural applications and flat panel displays. The architectural use of TCO is for energy efficient windows. Fluorine doped tin oxide (FTO), deposited using a pyrolysis process is the TCO usually finds maximum application. SnO2 also finds application ad coatings for windows, which are efficient in preventing radiative heat loss, due to low emissivity (0.16). Pyrolitic tin oxide is used in PV modules, touch screens and plasma displays. However indium tin oxide (ITO) is mostly used in the majority of flat panel display (FPD) applications. In FPDs, the basic function of ITO is as transparent electrodes. The volume of FPD’s produced, and hence the volume of ITO coatings produced, continues to grow rapidly. But the current increase in the cost of indium and the scarcity of this material created the difficulty in obtaining low cost TCOs. Hence search for alternative TCO materials has been a topic of active research for the last few decades. This resulted in the development of binary materials like ZnO, SnO2, CdO and ternary materials like II Zn2SnO4, CdSb2O6:Y, ZnSO3, GaInO3 etc. The use of multicomponent oxide materials makes it possible to have TCO films suitable for specialized applications because by altering their chemical compositions, one can control the electrical, optical, chemical and physical properties. But the advantages of using binary materials are the easiness to control the chemical compositions and depositions conditions. Recently, there were reports claiming the deposition of CdO:In films with a resistivity of the order of 10-5 ohm cm for flat panel displays and solar cells. However they find limited use because of Cd-Toxicity. In this regard, ZnO films developed in 1980s, are very useful as these use Zn, an abundant, inexpensive and nontoxic material. Resistivity of this material is still not very low, but can be reduced through doping with group-III elements like In, Al or Ga or with F [6]. Hence there is a great interest in ZnO as an alternative of ITO. In the present study, we prepared and characterized transparent and conducting ZnO thin films, using a cost effective technique viz Chemical Spray Pyrolysis (CSP). This technique is also suitable for large area film deposition. It involves spraying a solution, (usually aqueous) containing soluble salts of the constituents of the desired compound, onto a heated substrate.

Effect of Chromium Doping on the Diffraction Efficiency of Methylene Blue Sensitized PVA/Acrylamide Films

The effect of chromium doping on methylene blue sensitized Poly (vinyl alcohol)/Acrylamide was carried out by varying the ratios of Ammonium dichromate and methylene blue. In the case of films without ammonium dichromate, the diffraction efficiency was found to decrease on storage. On chromium doping the storage life was improved. Interestingly, a self-enhancement in efficiency was observed for a particular ratio of methylene blue and ammonium dichromate.

Engineering the Properties of Indium Sulfide for Thin Film Solar Cells by Doping

In the present work, structural, optical and electrical properties of indium sulfide are tuned by specific and controlled doping. Silver, tin, copper and chlorine were used as the doping elements. In2S3 thin films for the present study were prepared using a simple and low cost “Chemical Spray Pyrolysis (CSP)” technique. This technique is adaptable for large-area deposition of thin films in any required shape and facilitates easiness of doping and/or variation of atomic ratio. It involves spraying a solution, usually aqueous, containing soluble salts of the constituents of the desired compound onto a heated substrate. Doping process was optimized for different doping concentrations. On optimizing doping conditions, we tuned the structural, optical and electrical properties of indium sulfide thin films making them perform as an ideal buffer layer.

Fabrication of thin films and nano columnar structures of Fe-Ni amorphous alloys and modification of its surface properties by thermal annealing and swift heavy ion irradiation for tailoring the magnetic properties

Department of Physics, Cochin University of Science and Technology

Surface acidity and catalytic activity of mixed Fe-Al and Cr-Al pillared montmorillonites

The incorporation of transition metal oxide pillars such as those of iron and chromium along with Al2O3, pillars within the interlayers of a montmorillonite clay is investigated. The surface acidity of these catalysts has been evaluated for the first time employing the equilibrium adsorption of an electron donor, perylene, and the results are compared with those obtained by temperature programmed desorption of ammonia. The principle is based on the ability of a catalyst surface site to accept a single electron from an electron donor like perylene to form charge transfer complexes and the amount of adsorbed species is measured quantitatively by UV-vis spectroscopy. Fina1ly, an attempt has been made to correlate the acidity determined by the two independcnt methods and the catalytic activity of present systems in the benzoylation of toluene with benzoyl chloride. Incorporation of Fe and Cr has changed the properties of AI pitlared montmorillonite. Fe pillared systems have been found to be vcry good catalysts for benzoylation reaction

Effect of Te doping on thermal diffusivity of Bi2Se3 crystals: A study using open cell photoacoustic technique

An open cell configuration has been employed for the photoacoustic measurement of the thermal diffusivity of undoped Bi2Se3 crystals and Bi2Se3 crystals doped with various concentrations of Te. The amplitude of the photoacoustic signal obtained under heat transmission configuration as a function of chopping frequency is used to evaluate the numerical value of thermal diffusivity, α. Doped samples show a substantial reduction in the value of α compared to undoped samples. The variations in the thermal diffusivity of the doped samples are explained in terms of the phonon assisted heat transfer mechanism. It is seen that α is very sensitive to structural variations arising from doping. The experimentally observed results are correlated with X-ray diffraction studies.

Photoacoustic study of the effect of doping concentration on the transport properties of GaAs epitaxial layers

We report a photoacoustic (PA) study of the thermal and transport properties of a GaAs epitaxial layer doped with Si at varying doping concentration, grown on GaAs substrate by molecular beam epitaxy. The data are analyzed on the basis of Rosencwaig and Gersho’s theory of the PA effect. The amplitude of the PA signal gives information about various heat generation mechanisms in semiconductors. The experimental data obtained from the measurement of the PA signal as a function of modulation frequency in a heat transmission configuration were fitted with the phase of PA signal obtained from the theoretical model evaluated by considering four parameters—viz., thermal diffusivity, diffusion coefficient, nonradiative recombination time, and surface recombination velocity—as adjustable parameters. It is seen from the analysis that the photoacoustic technique is sensitive to the changes in the surface states depend on the doping concentration. The study demonstrates the effectiveness of the photoacoustic technique as a noninvasive and nondestructive method to measure and evaluate the thermal and transport properties of epitaxial layers.

Growth and characterisation of p-type delafossite transparent conducting thin films for heterojunction applications

In the present studies, various copper delafossite materials viz; CuAlO2, CuGaO2, CuFeO2 , CuGa1-xFexO2, CuYO2 and CuCaxY1-xO2 were synthesised by solid state reaction technique. These copper delafossite materials were grown in thin film form by rf magnetron sputtering technique. In general copper delafossites exhibit good optical transparency. The conductivity of the CuYO2 could be improved by Ca doping or by oxygen intercalation by annealing the film in oxygen atmosphere. It has so far been impossible to improve the p-type conductivity of CuGaO2 significantly by doping Mg or Ca on the Ga site. The ptype conductivity is presumed to be due to oxygen doping or Cu Vacancies [6]. Reports in literature show, oxygen intercalation or divalent ion doping on Ga site is not possible for CuGaO2 thin films to improve the p-type conductivity. Sintered powder and crystals of CuFeO2 have been reported as the materials having the highest p-type conductivity [14, 15] among the copper and silver delafossites. However the CuFeO2 films are found to be less transparent in the visible region compared to CuGaO2. Hence in the present work, the solid solution between the CuGaO2 and CuFeO2 was effected by solid state reaction, varying the Fe content. The CuGa1-xFexO2 with Fe content, x=0.5 shows an increase in conductivity by two orders, compared to CuGaO2 but the transparency is only about 50% in the visible region which is less than that of CuGaO2 The synthesis of α−AgGaO2 was carried out by two step process which involves the synthesis of β-AgGaO2 by ion exchange reaction followed by the hydrothermal conversion of the β-AgGaO2 into α-AgGaO2. The trace amount of Ag has been reduced substantially in the two step synthesis compared to the direct hydrothermal synthesis. Thin films of α-AgGaO2 were prepared on silicon and Al2O3 substrates by pulsed laser deposition. These studies indicate the possibility of using this material as p-type material in thin film form for transparent electronics. The room temperature conductivity of α-AgGaO2 was measured as 3.17 x 10-4 Scm-1and the optical band gap was estimated as 4.12 eV. A transparent p-n junction thin film diode on glass substrate was fabricated using p-type α-AgGaO2 and n-ZnO.AgCoO2 thin films with 50% transparency in the visible region were deposited on single crystalline Al2O3 and amorphous silica substrates by RF magnetron sputtering and p type conductivity of AgCoO2 was demonstrated by fabricating transparent p-n junction diode with AgCoO2 as p-side and ZnO: Al as n-side using sputtering. The junction thus obtained was found to be rectifying with a forward to reverse current of about 10 at an applied voltage of 3 V.The present study shows that silver delafossite thin films with p-type conductivity can be used for the fabrication of active devices for transparent electronics applications.

Highly conductive and transparent ZnO thin film using Chemical Spray Pyrolysis technique: Effect of doping and deposition parameters

In the present work we report the preparation details studies on ZnO thin films. ZnO thin films are prepared using cost effective deposition technique viz., Chemical Spray Pyrolysis (CSP). The method is very effective for large area preparation of the ZnO thin film. A new post-deposition process could also be developed to avoid the adsorption of oxygen that usually occurs after the spraying process i.e., while cooling. Studies were done by changing the various deposition parameters for optimizing the properties of ZnO thin film. Moreover, different methods of doping using various elements are also tried to enhance the conductivity and transparency of the film to make these suitable for various optoelectronic applications.

Coverage effects on the magnetism of Fe/MgO(001) ultrathin films

Different aspects of the structure-magnetism and morphology-magnetism correlation in the ultrathin limit are studied in epitaxial Fe films grown on MgO(001). In the initial stages of growth the presence of substrate steps, intrinsically higher than an Fe atomic layer, prevent the connection between Fe islands and hence the formation of large volume magnetic regions. This is proposed as an explanation to the superparamagnetic nature of ultrathin Fe films grown on MgO in addition to the usually considered islanded, or Vollmer-Weber, growth. Using this model, we explain the observed transition from superparamagnetism to ferromagnetism for Fe coverages above 3 monolayers (ML). However, even though ferromagnetism and magnetocrystalline anisotropy are observed for 4 ML, complete coverage of the MgO substrate by the Fe ultrathin films only occurs around 6 ML as determined by polar Kerr spectra and simulations that consider different coverage situations. In annealed 3.5 ML Fe films, shape or configurational anisotropy dominates the intrinsic magnetocrystalline anisotropy, due to an annealing induced continuous to islanded morphological transition. A small interface anisotropy in thicker films is observed, probably due to dislocations observed at the Fe¿MgO(001) interface.

Evidence of extended orientational order in amorphous Fe/Sm thin films

Amorphous thin films of Fe/Sm, prepared by evaporation methods, have been magnetically characterized and the results were interpreted in terms of the random magnets theory. The samples behave as 2D and 3D random magnets depending on the total thickness of the film. From our data the existence of orientational order, which greatly influences the magnetic behavior of the films, is also clear.

Ab initio study of MF2 (M=Mn, Fe, Co, Ni) rutile-type compounds using the periodic unrestricted Hartree-Fock approach

The ab initio periodic unrestricted Hartree-Fock method has been applied in the investigation of the ground-state structural, electronic, and magnetic properties of the rutile-type compounds MF2 (M=Mn, Fe, Co, and Ni). All electron Gaussian basis sets have been used. The systems turn out to be large band-gap antiferromagnetic insulators; the optimized geometrical parameters are in good agreement with experiment. The calculated most stable electronic state shows an antiferromagnetic order in agreement with that resulting from neutron scattering experiments. The magnetic coupling constants between nearest-neighbor magnetic ions along the [001], [111], and [100] (or [010]) directions have been calculated using several supercells. The resulting ab initio magnetic coupling constants are reasonably satisfactory when compared with available experimental data. The importance of the Jahn-Teller effect in FeF2 and CoF2 is also discussed.