Growth and characterization of nanostructured wide band gap semiconductors for optoelectronic applications

Department of Physics, Cochin University of Science and Technology

Investigations on the structural, optical and Magnetic properties of nanostructured cerium oxide in pure and doped forms and its polymer nanocomposiets

This thesis Entitled INVESTIGATIONS ON THE STRUCTURAL, OPTICAL AND MAGNETIC PROPERTIES OF NANOSTRUCTURED CERIUM OXIDE IN PURE AND DOPED FORMS AND ITS POLYMER NANOCOMPOSITES.Synthesis and processing of nanomatelials and nanostmctures are the essential aspects of nanotechnology. Studies on new physical properties and applications of nanomaterials and nanostructures are possible only when nanostructured materials are made available with desired size, morphology,crystal structure and chemical composition.Recently, several methods have been developed to prepare pure and doped CeO2 powder, including wet chemical synthesis, thermal hydrolysis, flux method, hydrothermal synthesis, gas condensation method, microwave technique etc. In all these, some special reaction conditions, such as high temperature, high pressure, capping agents, expensive or toxic solvents etc. have been involved.Another hi gh-li ght of the present work is room temperature ferromagnetism in cerium oxdie thin films deposited by spray pyrolysis technique.The observation of self trapped exciton mediated PL in ceria nanocrystals is another important outcome of the present study. STE mediated mechanism has been proposed for CeO2 nanocrystals based on the dependence of PL intensity on the annealing temperature. It would be interesting to extent these investigations to the doped forms of cerium oxide and cerium oxide thin films to get deeper Insight into STE mechanism.Due to time constraints detailed investigations could not be canied out on the preparation and properties of free standing films of polymer/ceria nanocomposites. It has been observed that good quality free standing films of PVDF/ceria, PS/C61‘l8, PMMA/ceria can be obtained using solution casting technique. These polymer nanocomposite films show high dielectric constant around 20 and offer prospects of applications as gate electrodes in metal-oxide semiconductor devices.

Evidence for polaron conduction in nanostructured manganese ferrite

Nanoparticles of manganese ferrite were prepared by the chemical co-precipitation technique. The dielectric parameters, namely, real and imaginary dielectric permittivity (ε and ε ), ac conductivity (σac) and dielectric loss tangent (tan δ), were measured in the frequency range of 100 kHz–8MHz at different temperatures. The variations of dielectric dispersion (ε ) and dielectric absorption (ε ) with frequency and temperature were also investigated. The variation of dielectric permittivity with frequency and temperature followed the Maxwell–Wagner model based on interfacial polarization in consonance with Koops phenomenological theory. The dielectric loss tangent and hence ε exhibited a relaxation at certain frequencies and at relatively higher temperatures. The dispersion of dielectric permittivity and broadening of the dielectric absorption suggest the possibility of a distribution of relaxation time and the existence of multiple equilibrium states in manganese ferrite. The activation energy estimated from the dielectric relaxation is found to be high and is characteristic of polaron conduction in the nanosized manganese ferrite. The ac conductivity followed a power law dependence σac = Bωn typical of charge transport assisted by a hopping or tunnelling process. The observed minimum in the temperature dependence of the frequency exponent n strongly suggests that tunnelling of the large polarons is the dominant transport process

Mechanism of ac conduction in nanostructured manganese zinc mixed ferrites

Mn1−xZnxFe2O4 nanoparticles (x = 0 to 1) were synthesized by the wet chemical co-precipitation technique. X-ray diffraction and transmission electron microscopy and high resolution transmission electron microscopy were effectively utilized to investigate the different structural parameters. The ac conductivity of nanosized Mn1−xZnxFe2O4 were investigated as a function of frequency, temperature and composition. The frequency dependence of ac conductivity is analysed by the power law σ(ω)ac = Bωn which is typical for charge transport by hopping or tunnelling processes. The temperature dependence of frequency exponent n was investigated to understand the conduction mechanism in different compositions. The conduction mechanisms are mainly based on polaron hopping conduction

Photoluminescence studies of spray pyrolytically grown nanostructured tin oxide semiconductor thin films on glass substrates

SnO2 nanocrystalline thin films were deposited on glass substrates by the spray pyrolysis technique in air atmosphere at 375, 400, 425, 450 and 500 ◦C substrate temperatures. The obtained films were characterized by using XRD. The room temperature photoluminescence (PL) spectra of these films have near band edge (NBE) and deep level emission under the excitation of 325 nm radiation. NBE PL peak intensity decreased consistently with temperatures for samples prepared at 400, 450 and 500 ◦C, while a sudden reduction in intensity is observed for the sample prepared at 425 ◦C. A similar effect was observed for the optical transmittance spectra. These effects can be explained on the basis of the change in population of oxygen vacancies as indicated by the change in a values

Investigations on the structural, optical and magnetic properties of nanostructured cerium oxide in pure and doped forms and its polymer nanocomposites

In recent years, nanoscience and nanotechnology has emerged as one of the most important and exciting frontier areas of research interest in almost all fields of science and technology. This technology provides the path of many breakthrough changes in the near future in many areas of advanced technological applications. Nanotechnology is an interdisciplinary area of research and development. The advent of nanotechnology in the modern times and the beginning of its systematic study can be thought of to have begun with a lecture by the famous physicist Richard Feynman. In 1960 he presented a visionary and prophetic lecture at the meeting of the American Physical Society entitled “there is plenty of room at the bottom” where he speculated on the possibility and potential of nanosized materials. Synthesis of nanomaterials and nanostructures are the essential aspects of nanotechnology. Studies on new physical properties and applications of nanomaterials are possible only when materials are made available with desired size, morphology, crystal structure and chemical composition. Cerium oxide (ceria) is one of the important functional materials with high mechanical strength, thermal stability, excellent optical properties, appreciable oxygen ion conductivity and oxygen storage capacity. Ceria finds a variety of applications in mechanical polishing of microelectronic devices, as catalysts for three-way automatic exhaust systems and as additives in ceramics and phosphors. The doped ceria usually has enhanced catalytic and electrical properties, which depend on a series of factors such as the particle size, the structural characteristics, morphology etc. Ceria based solid solutions have been widely identified as promising electrolytes for intermediate temperature solid oxide fuel cells (SOFC). The success of many promising device technologies depends on the suitable powder synthesis techniques. The challenge for introducing new nanopowder synthesis techniques is to preserve high material quality while attaining the desired composition. The method adopted should give reproducible powder properties, high yield and must be time and energy effective. The use of a variety of new materials in many technological applications has been realized through the use of thin films of these materials. Thus the development of any new material will have good application potential if it can be deposited in thin film form with the same properties. The advantageous properties of thin films include the possibility of tailoring the properties according to film thickness, small mass of the materials involved and high surface to volume ratio. The synthesis of polymer nanocomposites is an integral aspect of polymer nanotechnology. By inserting the nanometric inorganic compounds, the properties of polymers can be improved and this has a lot of applications depending upon the inorganic filler material present in the polymer.

Radiopaque materials from natural polymers: Special emphasis on chitosan and natural rubber

The present work is to impart radiopacity in various natural polymers like chitosan, natural rubber and derivatives of chitosan and to characterize it. This thesis collated the radiopaque properties of these radiopaque polymers and various technological applications in the medical field. The applications of radiopaque polymers leads to an exploitation of radiopaque properties like X-ray visibility, optical density, effective atomic number, attenuation coefficient of biopolymers like chitosan, chitosan formate, chitosan acetate, carboxy methyl chitosan and natural rubber. The radiopaqe properties of these materials highly depend upon the size, shape, amount of radiopacifier and crystallinity of the radiopaque material. Radiopaque chitosan microspheres were prepared by cross linking with glutaraldehyde followed by the encapsulation of barium sulpahte. The effect of different emulsion systems on the morphology of chitosan microspheres were studied. The study concentrates radiopaque natural rubber for shielding applications. It reveals that to improve the particle size, morphology and crystalline phase of the zinc oxide particles, a novel method for the preparation of zinc oxide is adopted. A detailed radiopacity study was done in natural rubber containing 100phr precipitated zinc oxide prepared from different zinc salts. One of the significant findings of this investigation is that NR vulcanizates containing precipitated zinc oxide (from zinc acetate) shows higher attenuation coefficient. These interesting findings reveal the applications of these natural radiopaque systems in various fields like surgical tools, medical tubings, catheters, radiation shielding,etc.

Conducting Polyaniline Composites as Microwave Absorbers

Conducting polymers are excellent microwave absorbers and they show technological advantage when compared with inorganic electromagnetic absorbing materials, being light weight , easily processable, and the ability of changing the electromagnetic properties with nature and amount of dopants, synthesis conditions, etc. In this paper we report the synthesis, dielectric properties, and expected application of conducting composites based on polyaniline (PAN). Cyclohexanone soluble conducting PAN composites of microwave conductivity 12.5 S/m was synthesized by the in situ polymerization of aniline in the presence of emulsion grade polyvinyl chloride. The dielectric properties of the composites, especially the dielectric loss, conductivity, dielectric heating coefficient , absorption coefficient, and penetration depth, were studied using a HP8510 vector network analyzer. The microwave absorption of the composites were studied at different frequency bands i.e, S, C, and X bands (2-12 GHz). The absorption coefficient was found to be higher than 200 m -' and it can be used for making microwave absorbers in space applications .

Conducting Polyaniline Composites as Microwave Absorbers

Conducting polymers are excellent microwave absorbers and they show technological advantage when compared with inorganic electromagnetic absorbing materials, being light weight , easily processable, and the ability of changing the electromagnetic properties with nature and amount of dopants, synthesis conditions, etc. In this paper we report the synthesis, dielectric properties, and expected application of conducting composites based on polyaniline (PAN). Cyclohexanone soluble conducting PAN composites of microwave conductivity 12.5 S/m was synthesized by the in situ polymerization of aniline in the presence of emulsion grade polyvinyl chloride. The dielectric properties of the composites, especially the dielectric loss, conductivity, dielectric heating coefficient , absorption coefficient, and penetration depth, were studied using a HP8510 vector network analyzer. The microwave absorption of the composites were studied at different frequency bands i.e, S, C, and X bands (2-12 GHz). The absorption coefficient was found to be higher than 200 m -' and it can be used for making microwave absorbers in space applications

Development of novel surface coatings based on acrylic copolymers

The present study describes the preparation of Vinyl acetate-Butyl acrylate copolymer lattices of varying compositions and solid contents by semicontinuous emulsion polymerization method. This copolymer lattices were used as binder to develop a new surface coating formulation. The properties of this surface coating were improved by using nano TiO2 colloidal sol as a pigment. Antimicrobial activity of surface coatings was improved by the addition of carboxymethyl chitosan as biocide. Uniformly dispersed tyre crumb was used to give a mat finish to the coating. The mechanical properties adhesive properties, thermal properties etc. of the coatings are presented in thesis.

Investigations on some technologically important polymer nanocomposite films and semi crystalline Polypyrrole films

The present work deals with investigations on some technologically important polymer nanocomposite films and semi crystalline polypyrrole films.The work presented in the thesis deals with the realization of novel polymer nanocomposites with enhanced functionalities and prospects of applications in the fields related to nanophotonics. The development of inorganic/polymer nanocomposites is a rapidly expanding multidisciplinary research area with profound industrial applications. The incorporation of suitable inorganic nanoparticles can endow the resulting nanocomposites with excellent electrical, optical and mechanical properties. The first chapter gives a general introduction to nanotechnology, nanocomposites and conducting polymers. It also emphasizes the significance of ZnO among other semiconductor materials, which forms the inorganic filler in the polymer nanocomposites of the present study. This chapter also gives general ideas on the properties and applications of conducting polymers with special reference to polypyrrole. The objectives of the present investigations are also clearly addressed in this chapter. The second chapter deals with the theoretical aspects and details of all the experimental techniques used in the present work for the synthesis of polymer nanocomposites and polypyrrole samples and their various characterizations. Chapter 3 is based on the preparation and properties of ZnO/Polystyrene nanocomposite film samples. The optical properties of these nanocomoposite films are discussed in detail.Chapter 4 deals with the detailed investigations on the dependence of the optical properties of ZnO/PS nanocomposite films on the size of the nanostructured ZnO filler material. The excellent UV shielding properties of these nanocomposite films form the highlight of this chapter. Chapter 5 gives a detailed analysis of the nonlinear optical properties of ZnO/PS nanocomposite films using Z scan technique. The effect of ZnO particle size in the composite films on the nonlinear properties is discussed. The present study involves two phases of research activities. In the first phase, the linear and nonlinear optical properties of ZnO/polymer nanocomposites are investigated in detail. The second phase of work is centered on the synthesis and related studies on highly crystalline polypyrrole films. In the present study, nanosized ZnO is synthesized using wet chemical method at two different temperatures

Physicochemical and Biochemical Characterization of Enzymes Immobilized on lnorganic Matrices

Biotechnology is currently considered as a useful altemative to conventional process technology in industrial and catalytic fields. The increasing awareness of the need to create green and sustainable production processes in all fields of chemistry has stimulated materials scientists to search for innovative catalysts supports. lmmobilization of enzymes in inorganic matrices is very useful in practical applications due to the preserved stability and catalytic activity of the immobilized enzymes under extreme conditions. Nanostructured inorganic, organic or hybrid organic-inorganic nanocomposites present paramount advantages to facilitate integration and miniaturization of the devices (nanotechnologies), thus affording a direct connection between the inorganic, organic and biological worlds. These properties, combined with good chemical stability, make them competent candidates for designed biocatalysts, protein-separation devices, drug delivery systems, and biosensors Aluininosilicate clays and layered double hydroxides, displaying, respectively, cation and anion exchange properties, were found to be attractive materials for immobilization because of their hydrophilic, swelling and porosity properties, as well as their mechanical and thermal stability.The aim of this study is the replacement of inorganic catalysts by immobilized lipases to obtain purer and healthier products.Mesocellular silica foams were synthesized by oil-in-water microemulsion templating route and were functionalized with silane and glutaraldehyde. " The experimental results from IR spectroscopy and elemental analysis demonstrated the presence of immobilized lipase and also functionalisation with silane and glutaraldehyde on the supports.The present work is a comprehensive study on enzymatic synthesis of butyl isobutyrate through esterification reaction using lipase immobilized onto mesocellular siliceous foams and montmorillonite K-10 via adsorption and covalent binding. Moreover, the irnrnobil-ization does not modify the nature of the kinetic mechanism proposed which is of the Bi-Bi Ping—Pong type with inhibition by n-butanol. The immobilized biocatalyst can be commercially exploited for the synthesis of other short chain flavor esters. Mesocellular silica foams (MCF) were synthesized by microemusion templating method via two different routes (hydrothermal and room temperature). and were functionalized with silane and glutaraldehyde. Candida rugosa lipase was adsorbed onto MCF silica and clay using heptane as the coupling medium for reactions in non-aqueous media. I From XRD results, a slight broadening and lowering of d spacing values after immobilization and modification was observed in the case of MCF 160 and MCF35 but there was no change in the d-spacing in the case of K-10 which showed that the enzymes are adsorbed only on the external surface. This was further confirmed from the nitrogen adsorption measurements

Optical and thermal characterization of dye intercalated montmorillonites and rare earth doped materials

The advent of high optical quality transparent nano—structured glasses, the so-called transparent glass ceramics or vitroceramics disclosed the possibility of producing nano-sized photonic devices based on rare-earth doped up—converters. Transparent glass ceramics have been investigated as hosts for lanthanide ions envisioning the production of materials that are easy to shape and with high performance for photonic applications. Rare earth doped glasses have been extensively studied due to their potential applications in optical devices such as solid state lasers and optical fibers. Various photothermal and optical techniques have been successfully applied for the thermal and optical characterization of these rare earth doped materials. In the present thesis, the effective thermal parameters like thermal diffusivity and thermal effusivity of complex materials for various applications have been investigated using photothermal methods along with their optical characterization utilising the common optical absorption as well as fluorescence spectroscopic techniques. These sensitive optical procedures are also essential for exploiting these materials for further photonic applications.

Preparation and Study of Optical Properties of CdS, CdS-TiO2 and CdS-Au Nanocomposites for Photonic Applications

Nanophotonics can be regarded as a fusion of nanotechnology and photonics and it is an emerging field providing researchers opportunities in fundamental science and new technologies. In recent times many new methodsand techniques have been developed to prepare materials at nanoscale dimensions. Most of these materials exhibit unique and interesting optical properties and behavior. Many of these have been found to be very useful to develop new devices and systems such as tracers in biological systems, optical limiters, light emitters and energy harvesters. This thesis presents a summary of the work done by the author in the field by choosing a few semiconductor systems to prepare nanomaterials and nanocomposites. Results of the study of linear and nonlinear optical properties of materials thus synthesized are also presented in the various chapters of this thesis. CdS is the material chosen here and the methods and the studies of the detailed investigation are presented in this thesis related to the optical properties of CdS nanoparticles and its composites. Preparation and characterization methods and experimental techniques adopted for the investigations were illustrated in chapter 2 of this thesis. Chapter 3 discusses the preparation of CdS, TiO2 and Au nanoparticles. We observed that the fluorescence behaviour of the CdS nanoparticles, prepared by precipitation technique, depends on excitation wavelength. It was found that the peak emission wavelength can be shifted by as much as 147nm by varyingthe excitation wavelengths and the reason for this phenomenon is the selective excitation of the surface states in the nanoparticles. This provided certain amount of tunability for the emission which results from surface states.TiO2 nanoparticle colloids were prepared by hydrothermal method. The optical absorption study showed a blue shift of absorption edge, indicating quantum confinement effect. The large spectral range investigated allows observing simultaneously direct and indirect band gap optical recombination. The emission studies carried out show four peaks, which are found to be generated from excitonic as well as surface state transitions. It was found that the emission wavelengths of these colloidal nanoparticles and annealed nanoparticles showed two category of surface state emission in addition to the excitonic emission. Au nanoparticles prepared by Turkevich method showed nanoparticles of size below 5nm using plasmonic absorption calculation. It was also found that there was almost no variation in size as the concentration of precursor was changed from 0.2mM to 0.4mM.We have observed SHG from CdS nanostructured thin film prepared onglass substrate by chemical bath deposition technique. The results point out that studied sample has in-plane isotropy. The relative values of tensor components of the second-order susceptibility were determined to be 1, zzz 0.14, xxz and 0.07. zxx These values suggest that the nanocrystals are oriented along the normal direction. However, the origin of such orientation remains unknown at present. Thus CdS is a promising nonlinear optical material for photonic applications, particularly for integrated photonic devices. CdS Au nanocomposite particles were prepared by mixing CdS nanoparticles with Au colloidal nanoparticles. Optical absorption study of these nanoparticles in PVA solution suggests that absorption tail was red shifted compared to CdS nanoparticles. TEM and EDS analysis suggested that the amount of Au nanoparticles present on CdS nanoparticles is very small. Fluorescence emission is unaffected indicating the presence of low level of Au nanoparticles. CdS:Au PVA and CdS PVA nanocomposite films were fabricated and optically characterized. The results showed a red-shift for CdS:Au PVA film for absorption tail compared to CdS PVA film. Nonlinear optical analysis showed a huge nonlinear optical absorption for CdS:Au PVA nanocomposite and CdS:PVA films. Also an enhancement in nonlinear optical absorption is found for CdS:Au PVA thin film compared to the CdS PVA thin film. This enhancement is due to the combined effect of plasmonic as well as excitonic contribution at high input intensity. Samples of CdS doped with TiO2 were also prepared and the linear optical absorption spectra of these nanocompositeparticles clearly indicated the influence of TiO2 nanoparticles. TEM and EDS studies have confirmed the presence of TiO2 on CdS nanoparticles. Fluorescence studies showed that there is an increase in emission peak around 532nm for CdS nanoparticles. Nonlinear optical analysis of CdS:TiO2 PVA nanocomposite films indicated a large nonlinear optical absorption compared to that of CdS:PVA nanocomposite film. The values of nonlinear optical absorption suggests that these nanocomposite particles can be employed for optical limiting applications. CdSe-CdS and CdSe-ZnS core-shell QDs with varying shell size were characterized using UV–VIS spectroscopy. Optical absorption and TEM analysis of these QDs suggested a particle size around 5 nm. It is clearly shown that the surface coating influences the optical properties of QDs in terms of their size. Fluorescence studies reveal the presence of trap states in CdSe-CdS and CdSe- ZnS QDs. Trap states showed an increase as a shell for CdS is introduced and increasing the shell size of CdS beyond a certain value leads to a decrease in the trap state emission. There is no sizeable nonlinear optical absorption observed. In the case of CdSe- ZnS QDs, the trap state emission gets enhanced with the increase in ZnS shell thickness. The enhancement of emission from trap states transition due to the increase in thickness of ZnS shell gives a clear indication of distortion occurring in the spherical symmetry of CdSe quantum dots. Consequently the nonlinear optical absorption of CdSe-ZnS QDs gets increased and the optical limiting threshold is decreased as the shell thickness is increased in respect of CdSe QDs. In comparison with CdSe-CdS QDs, CdSe-ZnS QDs possess much better optical properties and thereby CdSe-ZnS is a strong candidate for nonlinear as well as linear optical applications.