Thesis (PhD)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: This study developed and optimised zinc oxide (ZnO) nanowire-based nanogenerator. The nanogenerator works on the piezoelectric effect that is, a mechanical force is converted to an electrical voltage. The ZnO nanowires are piezoelectric and when any force is applied to the nanowires an output voltage is generated. This ZnO nanowire-based nanogenerator can be used to power small electronic devices, such as pacemakers. The nanogenerator can also be incorporated into clothes and shoes to generate electricity to charge a cell phone for example. The problem experienced currently is that the nanogenerator does not generate enough electricity to be of practical use and needs to be further optimised. Simulations and mathematical models were used to identify areas where the nanogenerator could be optimised in order to increase the output voltage. It is shown that the morphology of the nanowires can have a considerable effect on the output voltage. For this reason the growth of the nanowires was investigated first. Different methods were used to propagate the nanowires in order to select the method that, on average, has the highest output voltage. Accordingly, one parameter at a time and design of experiments were used to optimise the nanowire growth. Consequently, these two methods were used to optimise the growth parameters with the respect to the output voltage. The aqueous solution method was found to yield nanowires that give the highest generated output voltage. After growing over 600 nanowire samples, optimal growth parameters for this method were found. These optimal growth parameters were subsequently used to grow nanowires that were used to manufacture the nanogenerator. The nanowires were grown on a solid substrate and hence the nanogenerator was also manufactured on the solid substrate. Through various optimisations of the manufacturing process the maximum output voltage achieved was about 500 mV. However, this output voltage is too low to be of practical use, even though the output has been raised considerably. The main problem was found to be the fact that the contact between the nanowires and the electrode was weak due to contamination. A new method was therefore required where the electrode and the nanowires would be in proper contact to ensure that higher output voltages were achieved. Subsequently, a flexible nanogenerator was manufactured in order to solve this problem. Accordingly, the nanowires were grown on the flexible polyimide film and a buffer layer was then spun onto the flexible substrate, leaving only the nanowire tips exposed. The electrode was then sputtered on top of this buffer layer, covering the nanowire tips. This ensured proper contact between the nanowires and the electrode. The nanogenerator, which was manufactured with non-optimal growth parameters, gives a maximum voltage output of 1 V, double the maximum achieved with the solid nanogenerator. When the optimal growth parameters were used the output voltage was raised to 2 V. Various optimisation techniques were performed on the nanogenerator, including plasma treatment and annealing and the use of various materials in the buffer layer. Combining these optimisation methods subsequently led to an optimised nanogenerator that can generate an output voltage of over 5 V. This was achieved after over 1200 nanogenerators had been manufactured. However, the output voltage was not in a usable form. Circuitry was therefore developed to transform the voltage generated by the nanogenerator to a useable form. The best circuit, the LTC3588, was used to power an LED for 10 seconds. The completed device was found to achieve a power output of 0.3 mW, enough for small electronic devices. / AFRIKAANSE OPSOMMING: ‘n Sink-oksied (ZnO) nanodraad gebaseerde nanogenerator is ontwikkeld en geöptimeer. Die nanogenerator werk met behulp van die piezoelektriese effek - meganiese krag work omgesit in ‘n elektriese spanning. Die ZnO nanodrade is piezoelektries en wanneer ‘n krag op die drade aangewend word, word ‘n uittree spanning gegenereer. Die nanogenerator kan gebruik word om klein elektroniese toestelle, soos ‘n pasaangeër, van krag te voorsien. Die nanogenerator kan in klere en skoene geïnkorporeer word om elektrisiteit op te wek vir die laai van ‘n selfoon. Die probleem is egter dat die nanogenerator tans nie genoeg krag opwek om prakties van nut te wees nie en verdere optimasie word benodig. Simulasies en wikundige modelle work gebruik om areas te identifiseer waar die nanogenerator geöptimeer kan word, met die doel om die uittreespanning te verhoog. Dit word bewys dat die morfologie van die nanodrade ‘n groot effek het op die uittreespanning. Dus word die groei van die nanodrade eerste ondersoek. Verskillende metodes word gebruik om die nanodrade te groei en die beste metode, wat die hoogste uittreespanning op gemiddeld verskaf, word gekies. Een parameter op ‘n slag en ontwerp van eksperimente word gebruik om die nanodraad groei te optimeer. Die groei parameters word geöptimeer deur van die twee metodes gebruik te maak, en die optimeering word gedoen in terme van die uittreespanning. Die oplossing groei metode lei tot nanodrade wat die hoogste uittreespanning verskaf. Na oor die 600 nanodraad monsters gegroei is, is die optimale parameters gevind. Hierdie optimale parameters word uitsluitlik gebruik om die nanogenerator te vervaardig. Die nanodrade word op ‘n soliede substraat gegroei en dus word die nanogenerator op dieselfde soliede substraat vervaardig. Verskeie metodes is gebruik om die vervaardiging te optimeer en die hoogste uittreespanning wat bereik is, is 500 mV. Die uittreespanning is te laag om van praktiese nut te wees alhoewel dit heelwat verhoog is. Die grootste probleem is die swak kontak tussen die nanodrade en die elektrode, wat veroorsaak word deur kontaminasie. ‘n Nuwe metode word verlang wat beter kontak tussen die nanodrade en elektrode sal verseker. ‘n Buigbare nanogenerator is vervaardig om die probleem op te los. Die nanodrade word nou op ‘n buigbare film gegroei. ‘n Bufferlaag word tussen die nanodrade in gedraai, tot net die punte van die nanodrade nog sigbaar is. Die elektrode word bo-op die bufferlaag gedeponeer, wat behoorlike kontak tussen die nanodrade en elektrode verseker. Die nanogenerator wat met nie-optimale groei parameters vervaardig is, bereik ‘n uittreespanning van 1 V, dubbel die soliede nanogenerator. Met optimale groei parameters word die uittreespanning tot 2 V verhoog. Verskeie optimasie tegnieke word op die nanogenerator toegepas. Die metodes sluit in suurstof plasma behandeling, verhitting en die inkorporasie van verskillende materiale in die bufferlaag. ‘n Kombinasie van die metodes geïnkorporeer in een nanogenerator lei tot ‘n uittreespanning van 5 V. Die uittreespanning is bereik na oor die 1200 nanogenerators vervaardig is. The uittreespanning is nog nie in ‘n bruikbare vorm nie. Spesiale stroombane is ontwikkel wat die nanogenerator spanning omskakel na ‘n bruikbare vorm. Die beste stroombaan, die LTC3588, kan ‘n LED aanskakel vir 10 sekondes. The toestel kan ook 0.3mWuittreekrag voorsien, genoeg vir klein elektroniese toestelle om te werk.

Because of its excellent and unique physical properties, ZnO nanowires have been widely used in numerous scientific fields such as sensors, solar cells, nanogenerators, etc. Although it is believed that single crystal ZnO has a much higher electron transfer rate than TiO₂, it was found that ZnO nanowire-based dye-sensitized solar cells (DSSCs) have lower efficiencies than TiO₂ nanoparticle-based DSSCs because the density and surface area of ZnO nanowires are usually lower than that of TiO₂ nanoparticles, limiting the cell's light absorption, and because the open-root structure of ZnO nanowires results in electron back transfer that causes charge shortage of the cell. Here, experimental studies were performed that utilize strategic manipulations of the design of the ZnO nanowire based DSSCs in efforts to address and solve its key challenges. It was shown that by incorporating various blocking layers into the design of the cell, the performance of the DSSC can be improved. Specifically, by placing a hybrid blocking layer of TiO₂-P4VP polymer between the substrate and the ZnO nanowires, the conversion efficiency of the cell was 43 times higher than that of a cell without this blocking layer due to the reduction of electron back transfer. Furthermore, in efforts to improve the surface area of the ZnO nanowire array, unique three dimensional structures of ZnO nanowires were fabricated. It was found that by significantly improving the overall density and surface area of the ZnO nanowire array through distinctive hierarchal nanowire structures, the light harvesting efficiency and electron transport were enhanced allowing the DSSC to reach 5.20%, the highest reported value for 3D ZnO NW based DSSCs. Additionally, the development of a theoretical model was explored in efforts to investigate how the geometry of ZnO nanowires affects the incident photon-to-current conversion efficiency of 1D ZnO nanowire-based N719-sensitized solar cells at the maximum absorption wavelength of 543 nm.

Despite the many attractive features of carbon fiber reinforced polymers (FRPs) composites, they are prone to failure due to delamination. The ability to tailor the fiber/matrix interface FRPs is crucial to the development of composite materials with enhanced structural performance. In this dissertation, ZnO nanowires (NWs) were grown on the surface of carbon fibers utilizing low temperature hydrothermal synthesis technique prior to the hybrid composite fabrication. The scanning electron microscopy revealed that the ZnO nanowires were grown uniformly on the surface of the carbon fabric. The surface grown ZnO NWs functionally-graded the composite material properties and ensured effective load transfer across the interface. To assess the influence of the ZnO NWs growth, reference samples were also prepared by exposing the carbon fabric to the hydrothermal conditions. The damping properties of the hybrid ZnO NWs-CFRP composite were examined using the dynamic mechanical analysis (DMA) technique. The results showed enhanced energy dissipation within the hybrid composite. Quasi-static tensile testing revealed that the in-plane and out-of-plane strengths and moduli of the hybrid FRP composite were also boosted. The interlaminar shear strength (ILSS) measurements suggested the improvement in the mechanical properties of the composite to the enhanced adhesion between the ZnO nanowires and the other constituents (carbon fiber and epoxy). It was necessary thus, to utilize the molecular dynamics simulations (MD) to investigate the adhesion within the CFRP structure upon growing the ZnO nanowires on the surface of the carbon fibers. Molecular models of the carbon fibers, the epoxy matrix and the ZnO nanowires were built. The resulting molecular structures were minimized and placed within a simulation box with periodic boundary conditions. The MD simulations were performed using the force field COMPASS to account for the empirical energy interactions between the different toms in the simulation box. Proper statistical thermodynamics were employed to relate the dynamics of the molecular model to the macroscale thermodynamic states (pressure, temperature and volume). Per the computed potential energies of the different components of the composite, it was found that the polar surfaces in the ZnO structures facilitates good adhesion properties in the graphite-epoxy composite. Besides the attractive mechanical properties of the ZnO nanowires, their piezoelectric and semiconductor properties were sought to design an energy harvesting device. To ensure sufficient charges collection from the mechanically stressed individual ZnO nanowires, a copper layer was sputtered on top of the ZnO nanowires which introduced also a Schottky effect. The mechanical excitation was provided by exposing the device to different vibration environment. The output voltage and currents were measured at the conditions (in terms of frequency and resistive load). It was demonstrated that the electrical output could be enhanced by stacking up similar devices in series or in parallel. Finally, in an attempt to exploit the reversibility of the electromechanical coupling of the energy harvesting device, the constitutive properties of the hybrid ZnO nanowires-CFRP composite were estimated using the Mori-Tanaka approach. This approach was validated by a finite element model (FEM). The FEM simulations were performed on a representative volume element (RVE) to reduce the computational time. The results demonstrated that the mechanical properties of the hybrid ZnO NWs-CFRP composite were better than those for the baseline CFRP composite with identical carbon fiber volume fraction (but with no ZnO NWs) which confirmed the experimental findings. Furthermore, the electro-elastic properties of the hybrid composite were determined by applying proper boundary conditions to the FE RVE. The work outlined in this dissertation will enable significant advancement in the next generation of hybrid composites with improved structural and energy harvesting multifunctionalties. / Ph. D.

Cílem diplomové práce je popsat oxidaci nanotrubic sulfidu wolframičitého za zvýšených teplot v přítomnosti vodní páry. Na jejich povrchu se nejprve vytvoří nanočástice oxidu wolframu, ze kterých potom vyrůstají nanodráty. Na základě in-situ experimentů v rastrovacím elektronovém mikroskopu je navržen mechanismus reakce a ten je zjednodušeně popsán analyticky. Ukazuje se, že elektronový svazek má zásadní vliv na reakci.

Recently, there has been a growing interest in semiconductor and semiconducting oxide nanowires for applications in electronics, energy conversion, energy storage and optoelectronic devices such as field effect transistors, solar cells, Li- ion batteries, gas sensors, light emitting diodes, field emission displays etc. Semiconductor and semiconducting oxide nanowires have been synthesized widely by different vapor transport methods. However, conditions like high growth temperature, low vacuum, carrier gases for the growth of nanowires, limit the applicability of the processes for the growth of nanowires on a large scale for different applications. In this thesis work, studies have been made on the growth of semiconductor and semiconducting oxide nanowires at a relatively lower substrate temperature (< 500 °C), in a high vacuum (1× 10-5 mbar), without employing any carrier gas, by electron beam and resistive thermal evaporation processes. The morphology, microstructure, and composition of the nanowires have been investigated using analytical techniques such as SEM, EDX, XRD, XPS, and TEM. The optical properties of the films such as reflectance, transmittance in the UV-visible and near IR region were studied using a spectrophotometer. Germanium nanowires were grown at a relatively lower substrate temperature of 380-450 °C on Si substrates by electron beam evaporation (EBE) process using a Au-assisted Vapor-Liquid-Solid mechanism. High purity Ge was evaporated in a high vacuum of 1× 10-5 mbar, and gold catalyst coated substrates maintained at a temperature of 380-450 °C resulted in the growth of germanium nanowires via Au-catalyzed VLS growth. The influence of deposition parameters such as the growth temperature, Ge evaporation rate, growth duration, and gold catalyst layer thickness has been investigated. The structural, morphological and compositional studies have shown that the grown nanowires were single-crystalline in nature and free from impurities. The growth mechanism of Germanium nanowires by EBE has been discussed. Studies were also made on Silicon nanowire growth with Indium and Bismuth as catalysts by electron beam evaporation. For the first time, silicon nanowires were grown with alternative catalysts by the e-beam evaporation method. The use of alternative catalysts such as Indium and Bismuth results in the decrease of nanowire growth temperature compared to Au catalyzed Si nanowire growth. The doping of the silicon nanowires is possible with an alternative catalyst. The second part of the thesis concerns the growth of oxide semiconductors such as SnO2, Sn doped Indium oxide (ITO) nanowires by the electron beam evaporation method. For the first time, SnO2 nanowires were grown with a Au-assisted VLS mechanism by the electron beam evaporation method at a low substrate temperature of 450 °C. SEM, XRD, XPS, TEM, EDS studies on the grown nanowires showed that they were single crystalline in nature and free of impurities. The influence of deposition parameters such as the growth temperature, oxygen partial pressure, evaporation rate of Sn, and the growth duration has been investigated. Studies were also done on the application of SnO2 nanowire films for UV light detection. ITO nanowires were grown via a self-catalytic VLS growth mechanism by electron beam evaporation without the use of any catalyst at a low substrate temperature of 250-400 °C. The influence of deposition parameters such as the growth temperature, oxygen partial pressure, evaporation rate of ITO, and growth duration has been investigated. Preliminary studies have been done on the application of ITO nanowire films for transparent conducting coatings as well as for antireflection coatings. The final part of the work is on the Au-assisted and self catalytic growth of SnO2 and In2O3 nanowires on Si substrates by resistive thermal evaporation. For the first time, SnO2 nanowires were grown with a Au-assisted VLS mechanism by the resistive thermal evaporation method at a low substrate temperature of 450 °C. SEM, XRD, XPS, TEM, and EDS studies on the grown nanowires showed that they were single crystalline in nature and free of impurities. Studies were also made on the application of SnO2 nanowire films for methanol sensing. The self-catalytic growth of SnO2 and In2O3 nanowires were deposited in high vacuum (5×10-5 mbar) by thermal evaporation using a modified evaporation source and a substrate arrangement. With this arrangement, branched SnO2 and In2O3 nanowires were grown on a Si substrate. The influence of deposition parameters such as the applied current to the evaporation boat, and oxygen partial pressure has been investigated. The growth mechanism behind the formation of the branched nanowires as well as nanowires has been explained on the basis of a self-catalytic vapor-liquid-solid growth mechanism. The highlight of this thesis work is employing e-beam evaporation and resistive thermal evaporation methods for nanowire growth at low substrate temperatures of ~ 300-500 °C. The grown nanowires were tested for applications such as gas sensing, transparent conducting coatings, UV light detection and antireflection coating etc. The thesis is divided into nine chapters and each of its content is briefly described below. Chapter 1 In this chapter, a brief introduction is given on nanomaterials and their applications. This chapter also gives an overview of the different techniques and different growth mechanisms used for nanowires growth. A brief overview of the applications of semiconductors and semiconductor oxide nanowires synthesized is also presented. Chapter 2 Different experimental techniques employed for the growth of Si, Ge, SnO2, In2O3, ITO nanowires have been described in detail in this chapter. Further, the details of the different techniques employed for the characterization of the grown nanowires were also presented. Chapter 3 In this chapter, studies on the growth of Germanium nanowires by electron beam evaporation (EBE) are given. The influence of deposition parameters such as growth temperature, evaporation rate of germanium, growth duration, and catalyst layer thickness was investigated. The morphology, structure, and composition of the nanowires were investigated by XRD, SEM, and TEM. The VLS growth mechanism has been discussed for the formation of the germanium nanowires by EBE using Au as a catalyst. Chapter 4 This chapter discusses the growth of Si nanowires with Indium and Bismuth as an alternate to Au-catalyst by electron beam evaporation. The influence of deposition parameters such as growth temperature, Si evaporation rate, growth duration, and catalyst layer thickness has been investigated. The grown nanowires were characterized using XRD, SEM, TEM and HRTEM. The Silicon nanowires growth mechanism has been discussed. Chapter 5 This chapter discusses the Au-catalyzed VLS growth of SnO2 nanowires by the electron beam evaporation method as well as Antimony doped SnO2 nanowires by co-evaporation method at a low substrate temperature of 450 °C. The grown nanowires were characterized using XRD, SEM, TEM, STEM, Elemental mapping, HRTEM, and XPS. The effect of deposition parameters such as oxygen partial pressure, growth temperature, catalyst layer thickness, evaporation rate of Sn, and the growth duration of nanowires were investigated. The SnO2 nanowires growth mechanism has been explained. Preliminary studies were made on the possible use of pure SnO2 and doped SnO2 nanowire films for UV light detection. SnO2 nanowire growth on different substrates such as stainless steel foil (SS), carbon nanosheets films, and graphene oxide films were studied. SnO2 nanowire growth on different substrates, especially SS foil will be useful for Li-ion battery applications. Chapter 6 This chapter discusses the self catalyzed VLS growth of Sn doped Indium oxide (ITO) nanowires by the electron beam evaporation method at a low temperature of 250-400 °C. The grown nanowires were characterized using XRD, SEM, TEM, STEM, HRTEM, and XPS. The effect of deposition parameters such as oxygen partial pressure, growth temperature, evaporation rate of ITO, and the growth duration of the nanowires were investigated. Preliminary studies were also made on the possible use of self-catalyzed ITO nanowire films for transparent conducting oxides and antireflection coatings. ITO nanowire growth on different and large area substrates such as stainless steel foil (SS), and Glass was done successfully. ITO nanowire growth on different substrates, especially large area glass substrates will be useful for optoelectronic devices. Chapter 7 In this chapter, studies on the growth of SnO2 nanowires by a cost-effective resistive thermal evaporation method at a relatively lower substrate temperature of 450 °C are presented. The grown nanowires were characterized using XRD, SEM, TEM, HRTEM, and XPS. Preliminary studies were done on the possible use of SnO2 nanowire films for methanol sensing. Chapter 8 This chapter discusses the self-catalytic growth of SnO2 and In2O3 nanowires by resistive thermal evaporation. The nanowires of SnO2 and In2O3 were grown at low temperatures by resistive thermal evaporation using a modified source and substrate arrangement. In this arrangement, branched SnO2 nanowires, and In2O3 nanowires growth was observed. The grown nanowires were characterized using XRD, SEM, TEM, HRTEM, and XPS. The possible growth mechanism for branched nanowires growth has been explained. Chapter 9 The significant results obtained in the present thesis work have been summarized in this chapter.

The thesis is divided into two parts. The first part deals with the research work carried out on the synthesis and chemical modification of nanomaterials whereas the second part describes the preparation and characterisation of polymer films and their use as separation membranes. Part I of the thesis describing the synthetic strategies and chemical manipulation schemes employed on various types of nanomaterials is divided into six chapters. Chapter 1 describes a chemist’s approach towards synthesizing and tuning the properties of different classes of nanomaterials along with a brief account of their potential applications. Chapter 2 of the thesis describes the synthesis and characterization of various metal nanostructures (viz. nanoparticles, nanorods, nanosheets etc.) of nickel, ruthenium, rhodium and iridium using a solvothermal procedure. Chapter 3 deals with the nanoparticles of the novel oxide metal ReO3. ReO3@Au, ReO3@Ag, ReO3@SiO2 and ReO3@TiO2 core-shell nanostructures with ReO3 as the core nanoparticle have been synthesized through a two-step process and characterized. Dependence of the plasmon band of the ReO3 nanoparticles on the interparticle separation has been examined by incorporating the nanoparticles in various polymer matrices and the results compared with those obtained with gold nanoparticles. Chapter 4 presents the dispersion of nanostructures of metal oxides such as TiO2, Fe3O4 and ZnO in solvents of differing polarity (water, DMF and toluene) in the presence of several surfactants. In Chapter 5 of the thesis, fluorous chemical method of separation of metallic and semiconducting single-walled carbon nanotubes is described. This method involves the selective reaction of the diazonium salt of a fluorous aniline with the metallic nanotubes in an aqueous medium and subsequent extraction of the same in a fluorous solvent leaving the semiconducting nanotubes in the aqueous layer. Chapter 6 presents the studies on the interaction of single walled nanotubes and graphene with various halogen molecules (I2, IBr, ICl and Br2) of varying electron affinity probed by employing Raman spectroscopy and electronic absorption spectroscopy. Part II of the thesis describes a general method of fabricating ultrathin free-standing cross-linked polymer films and their subsequent use as separation membranes. A particular class of 1-D nanomaterials namely cadmium hydroxide nanostrands were used in this method throughout, to generate a sacrificial layer upon which the polymer films were generated.

One-dimensional (1D) nanostructures have gained tremendous attention over the last decade due to their wide range of potential applications. Particularly, ZnO 1D nanostructures have been investigated with great interest due to their versatility in synthesis with potential applications in electronics, optics, optoelectronics, sensors, photocatalysts and nanogenerators. The thesis deals with the challenges and the answer to grow ZnO 1D nanostructure by vapor phase transport (VPT) continuously without any length limitation. The conventional VPT technique has been modified for the non-catalytic growth of ultralong ZnO 1D nanostructures and branched structures in large area with controllable aspect ratio. It has been shown that the aspect ratio can be controlled both by thermodynamically (temperature) and kinetically (vapour flux). The thesis also deals with the fabrication of carbon nanotube (CNT) -ZnO based multifunctional devices and the field emission performance of ZnO nanowires by employing various strategies. The entire thesis has been organised as follows: Chapter 1 deals with Introduction. In this chapter, importance of ultralong nanowires and significance of ultralong ZnO nanowires has been discussed. Various efforts to grow ultralong ZnO nanowire with their advantages and disadvantages have been summarised. Lastly the significance of forming ZnO nanowires based nano hybrid structures and importance of doping in ZnO nanowires and has also been discussed. Chapter 2 deals with experimental procedure and characterization. In this chapter, a single step VPT method for the growth of ultralong ZnO nanowires that incorporates local oxidation barrier for the source has been described. The synthesized nanowires were characterised by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman & photoluminescence. Chapter 3 deals with growth of ZnO nanowires, controlling the aspect ratio of ZnO nanowires, and role of other experimental aspects. In this chapter, a way to grow nanowires continuously without any apparent length limitation, a way to control the diameter of the nanowires kinetically without catalyst particle or seed layer and obtaining smaller diameter of the nanowires by non-catalytic growth as compared to that set by the thermodynamic limit has been discussed. Furthermore, the significance and importance of local oxidation barrier on source for protecting them from degradation, ensuring the continuous supply of vapour and enabling the thermodynamically and kinetically controlled growth of nanowires has been discussed. Lastly, the scheme for large area deposition and a method to use same source material for several depositions has been presented. Chapter 4 deals with multifunctional device based on CNT -ZnO Nanowire Hybrid Architectures same device can be used as a rectifier, a transistor and a photodetector. In this chapter, the fabrication of CNT arrays-ZnO nanowires based hybrid architectures that exhibit excellent high current Schottky like behavior with p-type conductivity of ZnO has been discussed. CNT-ZnO hybrid structures that can be used as high current p-type field effect transistors (FETs) and deliver currents of the order of milliamperes has been presented. Furthermore, the p-type nature of ZnO and possible mechanism for the rectifying characteristics of CNT-ZnO has been discussed. Lastly, the use of hybrid structures as ultraviolet detectors where the current on-off ratio and the response time can be controlled by the gate voltage has been presented and also an explanation for photoresponse behaviour has been provided. Chapter 5 deals with the substrate-assisted doping of ZnO nanowires grown by this technique. In this chapter, the non-catalytic growth of ZnO nanowires on multiwalled carbon nanotubes (MWCNTs) and soda lime glass (SLG) with controlled aspect ratio has been presented. The elemental mapping to confirm the presence and distribution of carbon and sodium in ZnO nanowires and the transport studies on both carbon and sodium doped ZnO has also been presented. Furthermore the stability of carbon doped ZnO has also been presented. Lastly, the advantage of growing ZnO nanowires on MWCNTs and overall advantage associated with this technique has been discussed. Chapter 6 deals with formation of ZnO nanowire branched structures. In this chapter, a possibility to grow ZnO nanowires on already grown ZnO nanowires has been demonstrated. The formation of branched structure during multiple growth of ZnO nanowire on ZnO nanowire has been presented and evolution of aspect ratio in these branched structures has been discussed. Furthermore, the advantage of using ZnO branched structures and also the ZnO nanoneedles on MWCNT mat for field emission has been presented. Chapter 7 summarizes all the findings of the thesis.

Li-ion thin film battery technology has attracted much attention in recent years due to its highest need in portable electronic devices. Development of new materials for lithium ion battery (LIB) is very crucial for enhancement of the performance. LIB can supply higher energy density because Lithium is the most electropositive (-3.04V vs. standard hydrogen electrode) and lightest metal (M=6.94 g/mole). LIBs show many advantages over other kind of batteries such as, high energy density, high power density, long cycle life, no memory effect etc. The major work presented in this thesis is on the development of nanostructured materials for anode of Li-ion battery. It involves the synthesis and analysis of grapheme nanosheet (GNS) and its performance as anode material in Li ion battery. We studied the synthesis of GNS over different substrates and performed the anode studies. The morphology of GNS has great impact on Li storage capacity. Tin and Tin oxide nanostructures have been embedded in the GNS matrix and their electrochemical performance has been studied. Chapter 1 gives the brief introduction about the Li ion batteries (LIBs), working and background. Also the relative advantages and characterization of different electrode materials used in LIBs are discussed. Chapter 2 discusses various experimental techniques that are used to synthesize the electrode materials and characterize them. Chapter3 presents the detailed synthesis of graphene nanosheet (GNS) through electron cyclotron resonance (ECR) microwave plasma enhanced chemical vapor deposition (ECR PECVD) method. Various substrates such as metallic (copper, Ni and Pt coated copper) and insulating (Si, amorphous SiC and Quartz) were used for deposition of GNS. Morphology, structure and chemical bonding were analyzed using SEM, TEM, Raman, XRD and XPS techniques. GNS is a unique allotrope of carbon, which forms highly porous and vertically aligned graphene sheets, which consist of many layers of graphene. The morphology of GNS varies with substrate. Chapter 4 deals with the electrochemical studies of GNS films. The anode studies of GNS over various substrates for Li thin film batteries provides better discharge capacity. Conventional Li-ion batteries that rely on a graphite anode have a limitation in the capacity (372 mAh/g). We could show that the morphology of GNS has great effect in the electrochemical performance and exceeds the capacity limitation of graphite. Among the electrodes PtGNS shown as high discharge capacity of ~730 mAh/g compare to CuGNS (590 mAh/g) and NiGNS (508 mAh/g) for the first cycle at a current density of 23 µA/cm2. Electrochemical impedance spectroscopy provides the various cell parameters of the electrodes. Chapter 5 gives the anodic studies of Tin (Sn) nanoparticles decorated over GNS matrix. Sn nanoparticles of 20 to 100nm in size uniformly distributed over the GNS matrix provides a discharge capacity of ~1500 mAh/g mAh/g for as deposited and ~950 mAh/g for annealed Sn@GNS composites, respectively. The cyclic voltammogram (CV) also shows the lithiation and delithiation process on GNS and Sn particles. Chapter 6 discusses the synthesis of Tinoxide@GNS composite and the details of characterization of the electrode. SnO and SnO2 phases of Tin oxide nanostructures differing in morphologies were embedded in the GNS matrix. The anode studies of the electrode shows a discharge capacity of ~1400 mAh/g for SnO phase (platelet morphology) and ~950 mAh/g for SnO2 phase (nanoparticle morphology). The SnO phase also exhibits a good coulumbic efficiency of ~95%. Chapter 7 describes the use of SnO2 nanowire attached to the side walls of the GNS matrix. A discharge capacity of ~1340 mAh/g was obtained. The one dimensional wire attached to the side walls of GNS film and increases the surface area of active material for Li diffusion. Discharge capacity obtained was about 1335 mAhg-1 and the columbic efficiency of ~86% after the 50th cycle. The research work carried out as part of this thesis, and the results have summarized in chapter 8.