A simulation methodology to model contact and non-contact microscopy measurements has been developed within a 3-D finite element commercial device simulator by Silvaco. The tip-sample system is modelled self-consistently including tip-induced band bending and realistic tip shapes. When modelling scanning tunnelling microscopy, the resulting spectra from III-V semiconductors show good agreement with experimental results and a model based on the Bardeen tunnelling approach. We have found that the image force induced barrier lowering increases the tunnelling current by three orders of magnitude when tunnelling in to the sample valence band, and by six orders of magnitude when tunnelling in to the sample conduction band. We have shown that other models which use a single weighting factor to account for image force in the conduction and valence bands are likely to underestimate the valence band current by three orders of magnitude. The role of probe shank oxide formed at the tip in air has been examined by carrying out contact and non-contact current-voltage simulations of GaAs when the probe oxide has been controllably reduced. For both contact and non-contact simulations, the contact resistance change due to oxide is dependent on polarity and as confirmed experimentally. An electrostatic tip apex interaction with an In203 thin film transistor under operation is studied using a combination of experimental electrostatic force microscopy measurements and simulations. An error in the surface potential near the drain electrode is observed in simulations due to the tip induced band bending. Two point probe measurements on ZnO nanowires and 3-D transport simulations reveal the change in the electrical behaviour of nanoscale contacts from Schottky-like to Ohmic-like when the size of Au catalyst particles is changed at the ends of free-standing ZnO nanowires in relation to the nanowire cross-section. In addition, a geometry dependent current crowding effect was analysed in the combination with self-heating calculations. Finally, we have investigated carrier confinement at the ZnO/GaZnO interface due to band offset and polarization effects. We have found that this material system is a good candidate for polarization heterostructure field effect transistors.

No description available.

Structural engineering plays an essential role in controlling the optical properties of nanostructures, which are of fundamental and practical interest in nanoscience and technology. In this study, two kinds of nanostructural engineering were investigated systematically to enrich nano-optics research: structural helicity was imposed on plasmonic nanoparticles (NPs) with chiroptical activity engineerable in the ultraviolet (UV)-visible region, and porosification was imposed on silicon nanowires (SiNWs) to tune optical interaction and photoluminescence (PL).. The generation of helical metamaterials, which have strong, engineerable chiroptical activity in the UV-visible region, has attracted increasing attention due to the manipulation of the circular polarization state of light to develop diverse homochirality-associated bio-applications. Glancing-angle deposition with fast substrate rotation is performed to generate plasmonic helical NPs (PhNPs) with a helical pitch (P) of less than 10 nm, which is so much smaller than the wire diameter (d) that the PhNPs appear to be achiral NPs. The PhNPs exhibit chiroptical activity that originates intrinsically from hidden helicity, characterized by circular dichroism (CD). With an increase of P from 3 to 66 nm, the plasmonic CD signals barely shift but show a logarithmic amplification. PhNPs made of aluminum, silver, and copper exhibit a stable chiroptical response from the deep UV (~220 nm) region to the visible region. When an achiral plasmonic nanostructure guest is coated on a PhNP host (i.e., a chiral host@achiral guest nanostructure is created), the achiral guest becomes chiroptically active due to helicity transfer from the chiral host to the achiral guest. Such a helicity transfer can be generally adapted to diverse plasmonic metals to tailor the plasmonic chiroptical response flexibly in the UV-visible region. Furthermore, an amplification of the near-field optical chirality induced by the PhNPs would pave a novel way to performing asymmetric syntheses, for which investigations are currently lacking. Silver PhNPs are used to effectively mediate the enantioselective photocyclodimerization of 2-anthracenecarboxylate: left-handed silver PhNPs lead to a positive ee (enantiomeric excess) value, and right-handed silver PhNPs give rise to a negative ee value. The enantioselectivity is enhanced with a decreasing P. The PhNP-mediated enantioselective photocyclodimerization is ascribed to the synergistic contribution from chirally helical surface-induced enantioselective adsorption of 2-anthracenecarboxylate and chiroptically active nanoplasmon-enhanced optical chirality of near-field circularly polarized light.. Metal-assisted chemical etching (MACE) is carried out to generate mesoporous SiNWs (mp-SiNWs) with mesopores from 2 to 50 nm. The porosification imposes two prominent properties onto SiNWs: a high surface-to-volume ratio and quantum confinement ascribed to the shrinkage of silicon skeletons. Hence, engineering the porosity of SiNWs is of fundamental importance. Here, a new method is devised to reduce the porosity of mp-SiNWs without changes in the MACE conditions. After generating the mp-SiNWs with high porosity, the mp-SiNWs are removed from the mother Si wafers with sticky tape, followed by MACE under the same conditions to produce low-porosity mp-SiNWs. Less porous mp-SiNWs reduce optical scattering from the porous Si skeletons and vertically protrude on the wafer without aggregation to facilitate optical trapping. Consequently, low-porosity mp-SiNWs effectively reduce UV-visible reflection loss. Furthermore, optical applications require surface modification of mp-SiNWs with functional chemicals, which has a prerequisite to passivate mp-SiNWs with H-termination using 5% hydrogen fluoride. 40% NH4F, which has been widely used to passivate Si(111) wafers with H-termination, tends to unexpectedly etch mp-SiNWs attributed to surface F-termination caused by the nucleophilic attack of F− anions to Si atoms. It has been used to study systematically the NH4F-etching rate as a function of the doping levels of SiNWs, surface crystalline orientations, and porosity. At a modest temperature of 110°C, 1,4-diethynylbenzene (DEBZ) is grafted via monosilylation grafted on H-terminated mp-SiNWs. The modified mp-SiNWs with chemically active monolayers is facilely subjected to further chemical modification and surface functionalization. In addition, the monosilylation encodes mp-SiNWs with PL of DEBZ, opening a door to flexible engineering of PL of mp-SiNWs for optoelectronic and bio-detection applications.

This thesis is based on research in Cu-catalyzed electrophilic trifluoromethylation and exploiting Cu/Cu2O nanowires with novel catalytic reactivity for developing of catalytic and greener synthetic methods. A large number of biological active pharmaceuticals and agrochemicals contain fluorine substituents (-F) or trifluoromethyl groups (-CF3) because these moieties often result in profound changes of their physical, chemical, and biological properties, such as metabolic stability and lipophilicity. For this reason, the introduction of fluorine or trifluoromethyl groups into organic molecules has attracted intensive attention. Among them, transition metal-catalyzed trifluoromethylation reactions has proved to be an efficient and reliable strategy to construct carbon-fluorine (C-F) and carbontrifluoromethyl (C-CF3) bond. We have developed a catalytic process for the first time for trifluoromethylation of terminal alkynes with Togni’s reagent, affording trifluoromethylated acetylenes in good to excellent yields. The reaction is conducted at room temperature and exhibits tolerance to a range of functional groups. Derived from this discovery, the extension of work of copper catalyzed electrophilic trifluoromethylation were investigated which include the electrophilic trifluoromethylation of arylsulfinate salts and electrophilic trifluoromethylation of organotrifluoroborates. Because of growing environmental concern, the development of greener synthetic methods has drawn much attention. Nano-sized catalysts are environment-friendly and an attractive green alternative to the conventional homogeneous catalysts. The nano-sized catalysts can be easily separated from the reaction mixture due to their insolubility and thus they can be used recycled. Notably, because of the high reactivities of nano-sized metal catalysts, the use of ligands can be avoided and the catalysts loadings can be reduced greatly. Moreover, the nano-sized catalysts can increase the exposed surface area of the active component, thereby enhancing the contact between reactants and catalyst dramatically. Based on the above-mentioned concepts and with the aim of achieving one “green and sustainable” approach, C-S bond formation and click reactions catalyzed by Cu/Cu2O nanowires were investigated. It was found that the recyclable core-shell structured Cu/Cu2O nanowires could be applied as a highly reactive catalysts for the cross-coupling reaction between aryl iodides and the cycloaddition of terminal alkynes and azides under ligand-free conditions. Furthermore, these results were the first report for the crosscoupling reaction and click reaction catalyzed by one-dimensional (1D) copper nanowires.

An economically reliable technique for the synthesis of silicon nanowire was developed using silicon chloride as source material. The 30-40 micron long nanowires were found to have diameters ranging from 40 – 100 nm. An amorphous oxide shell covered the nanowires, post-growth. Raman spectroscopy confirmed the composition of the shell to be silicon-dioxide. Photoluminescence measurements of the as-grown nanowires showed green emission, attributed to the presence of the oxide shell. Etching of the oxide shell was found to decrease the intensity of green emission. n-type doping of the silicon nanowires was achieved using antimony as the dopant. The maximum dopant concentration was achieved by post-growth diffusion. Intrinsic nanowire parameters were determined by implementation of the as-grown and antimony doped silicon nanowires in field effect transistor configuration.

No description available.

Various techniques to synthesize nanowires and nanotubes as a function of growth temperature and time were investigated. These include growth of nanowires by a chemical vapor deposition (CVD) system using vapor-liquid-solid (VLS) growth mechanism and electro-chemical synthesis of nanowires and nanotubes. Narrow band gap InSb Eg = 0.17 eV at room temp) nanowires were successively synthesized. Using a phase diagram, the transition of the nanowire from metallic- semiconducting- semi-metallic phase was investigated. A thermodynamic model is developed to show that the occurrence of native defects in InSb nanowires influenced by the nanowire growth kinetics and thermodynamics of defect formation. Wide band gap ZnO (Eg = 3.34 eV) and In2O3 (3.7 eV) were also synthesized. ZnO nanowires and nanotubes were successfully doped with a transition metal Fe, making it a Dilute Magnetic Semiconductor of great technological relevance. Structural and electronic characterizations of nanowires were studied for different semiconducting, metallic and semi-metallic nanowires. Electron transport measurements were used to estimate intrinsic material parameters like carrier concentration and mobility. An efficient gas sensing device using a single In2O3 nanowire was studied and which showed sensitivity to reducing gas like NH3 and oxidizing gas like O2 gas at room temperature. The efficiency of the gas sensing device was found to be sensitive to the nature of contacts as well as the presence of surface states on the nanowire.

No description available.

The principal aim of this thesis is to study the electrical transport properties of metal nanowires. Specifically, we have focussed on investigating the resistance fluctuations of Ag and Cu nanowires of diameters ranging from 15nm to 200nm and studied the instabilities that set in when the diameter is reduced below a certain range. The nanowires were grown electrochemically inside polycarbonate and alumina templates. X-ray diffraction studies on the samples showed the presence of a HCP 4H phase in the Ag nanowires in addition to the usual FCC phase, which is seen in bulk Ag. The relative ratios of these two phases were a maximum for nanowires of diameter 30nm. The X-ray diffraction studies also showed that the samples were of high chemical purity. TEM studies revealed that the wires are single crystalline in nature. Once the wires are released from the template, the wires of diameter 15nm were seen to break down spontaneously into globules due to Rayleigh instability. Wires of larger diameter tended to neck down to smaller radius but did not break down completely into globules. Both the Ag and Cu nanowire arrays had a fairly linear temperature dependence of resistance down to about 100K and reached a residual resistance below 40-50K. The temperature dependence of resistance could be fitted to a Bloch-Grüneisen formula over the entire temperature range. We found that n = 5 gave the best fit for the wires of all diameters showing that the dominant contribution to the temperature dependence of the resistivity in theses nanowires come from electron-acoustic phonon interactions. The resistivities of the wires were seen to increase as the wire diameter was decreased. This increase in the resistivity of the wires could be attributed to surface scattering of conduction electrons. In nanowires of diameter 15nm of both Ag and Cu, the relative variance of resistance fluctuations <(ΔR)2>/R2 showed a prominent peak at around ~ 220K for the Ag nanowire and ~ 260K for the Cu wire. Ag wires of diameter 20nm showed a much-reduced peak in noise at a somewhat higher temperature while this feature was completely absent in wires of larger diameter as also for the reference Ag film. The noise in wires of diameter larger than 20nm was similar to that of the reference film. For wires of diameter 15nm as we approach T*, the power spectral density showed a severe deviation from 1/f nature. We could establish that the extra fluctuation seen in the nanowires of the narrowest diameters could originate from the Rayleigh instability. The measured resistance fluctuation was found to have a magnitude similar to that estimated from a simple model of a wire showing volume preserving fluctuation. In the temperature range T ≤ 100K we observed very large non-Gaussian resistance fluctuations in a narrow temperature range for Ag and Cu wires of diameter 30nm with the fluctuations becoming much smaller as the diameter of the wires deviated from 30nm. In wires of diameter larger than 50nm the noise was almost independent of temperature in this range. The power spectrum of the resistance fluctuations also developed a large additional low frequency component near TP. We could establish that the appearance of this noise at a certain temperature (~30 – 50K) is due to the onset of martensite strain accommodation in these nanowires. To summarize, we measured the resistance and resistance fluctuations of Ag and Cu nanowires of diameters ranging from 15nm to 200nm in the temperature range 4.2-300K. The temperature dependence of resistance could be fitted to a Bloch-Grüneisen formula over the entire temperature range of measurement (4.2K-300K). The contribution of electron-phonon scattering to the resistivity was found to be similar to that of bulk. The defect free nature of our samples allowed us to identify two novel sources of noise in these nanowires. At high temperatures Rayleigh instability causes the noise levels in wires of diameter around 15nm to increase. At lower temperatures the formation of martensite state leads to an increase in noise in wires of small diameters.

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.