A promising approach investigated here is to utilize thin film multilayer structures where the thickness of a catalyst layer at an exposed edge of photolithographically defined pattern determines the diameter of the nanotubes/nanowires grown from it. This can in turn be incorporated into photolithographically defined post structures resulting in an array of suspended nanowires for line-of-site shadow lithography. Success of the diameter control approach has been shown by selectively growing carbon nanotubes (CNTs) from narrow lines (12-60 nm) of SiO2, Fe, Ni, Co on micron-scale patterned substrates in a ferrocene or nonferrocene catalyzed CVD process. In addition, the concept has been extended to VS growth of CuO nanowires and VLS growth of ZnO nanowires from an exposed edge in a Al2O3/Cu(40-100 nm)/Al2O3 and Al2O3/Au(10 nm)/Al2O3 thin film multilayer structures. The exposed middle layer of patterned thin-film multilayer acts as a nm-scale wide selective growth area. The resultant CNT/nanowire diameter is directly related to the catalyst/catalyst support size. Growth kinetic studies of CuO nanowires from a thin film multilayer structure indicate diffusion controlled process. Dispersion of CNTs between lithographically defined trenches of width of 200 nm and depth of 500 nm when coupled with line-of-site deposition resulted in nm-scale line underneath the suspended CNT. The width of the resulting shadow is nearly a simple function of CNT/nanowire diameter, incident evaporation angle, and height of CNT above the substrate in a line-of-site evaporation geometry. Another promising approach to control the placement of nanotubes/nanowires is the selective functionalization of only their tips followed by selfassembly onto chemically patterned substrates. Towards this goal, arrays of aligned CNTs were impregnated with polystyrene to form aligned CNT membranes. These CNT membranes were also studied for gas and ionic transport studies. Different functionalization chemistry was performed on each side of the membrane. After dissolution of polymer matrix, a suspension of CNTs with different functionality at each tip was formed, allowing for sophisticated selfassembled architectures.

We are surrounded by enormous amounts of ambient mechanical energy that goes to waste such as rain drops, human footfalls, air flow, ocean waves, just to name a few. If such otherwise wasted mechanical energy can be effective converted into electricity, self-powered electronics are very likely to be realized, which can address the limitations of traditional power supplies in many cases, such as wireless sensor networks. Here in this work, two types of energy-harvesting nanogenerators (NGs) based were studied. For piezoelectric nanogenerators, zinc oxide (ZnO) nanowires (NWs) were used as building blocks to develop integrated NGs based on a number of ZnO NWs instead of a single NW. Two types of integrated NGs were developed, which consist of lateral NW arrays and vertical NW arrays. The electric output power was substantially enhanced compared to the design with a single NW. For triboelectric nanogenerators, triboelectric effect was innovatively used as an effective means of harvesting mechanical energy. The operating principle can be explained by the coupling between triboelectric and electrostatic effect. Two types of operating modes were invented, i.e. contact mode and sliding mode. Triggered by commonly available ambient mechanical energy such as footfalls, the maximum output power reached up to 1.2 W. More importantly, self-powered systems were built by using the NG as a power source. It can provide real time power for up to 600 commercial LED bulbs. This research not only provides the fundamentals for NGs but also demonstrates the practicability of using the self-powered technology in our daily life.

The goal of this dissertation work was to develop pulsed terahertz radiation techniques and use them to study different properties of the semiconductor materials and semiconductor devices. Three groups of materials were investigated: GaAsBi, GaAs nanowires, copper-indium chalcogenide. The used techniques are THz-TDS, optical pump – THZ probe, optical pump – optical probe and THz excitation spectral measurements. The main results that were presented in this dissertation are the following: thermal annealing has resulted in the shortening of electron lifetime in GaAsBi to picosecond values, which is important achievement for the application of this material in THz range components. In GaAsBi layers with larger than 10% Bi content absorption bleaching recovering on the picosecond time scale and its saturation can be realized when the wavelengths of the optical signals are as long as 1600 nm. The results of these studies can be applied in the production of SESAM with bismide absorption layer. The samples with GaAs nanowires emit THz radiation several times better than the bulk GaAs substrates due to enhanced light absorption because of localized surface plasmon resonances in GaAs nanowires. THz emission efficiency from thin copper-indium chalcogenide layers strongly depends on their stoichiometry and on the parameters of the top transparent contact layers, thus it can be used for the mapping of built-in electric fields in solar cells made from these layers. / Šio darbo tikslas buvo susipažinti su terahercinių impulsų generavimo ir detektavimo būdais, įsisavinti įvairias terahercinių impulsų panaudojimo metodikas bei pritaikyti jas puslaidininkių medžiagų ir puslaidininkinių prietaisų tyrimui. Buvo tirtos trys medžiagų grupės: GaAsBi, GaAs nanovielutės ir Cu – In chalkogenidai. Tyrimui buvo naudojamos: THz – TDS, optinio žadinimo – THz zondavimo, optinio žadinimo – optinio zondavimo bei THz sužadinimo spektroskopijos metodikos. Pagrindiniai rezultatai aprašyti disertacijoje yra šie: GaAsBi bandinių atkaitinimas stipriai sumažino krūvininkų gyvavimo trukmes, kas yra naudinga THz komponentų gamyboj. Optinio praskaidrėjimo efektas ir pikosekundžių eilės krūvininkų gyvavimo trukmės GaAsBi epitaksiniuose sluoksniuose su 10% ir daugiau Bi atomų stebimas žadinant juos optine spinduliuote, kurios bangos ilgiai siekia iki 1600 nm. Šios GaAsBi bandinių savybės leidžia juos priakyti įsisotinančių sugėriklių veidrodžių gamyboje. Bandiniai su GaAs nanovielutėmis emituoja THz spinduliuotę kelis kartus geriau nei GaAs padėklas, dėl padidėjusios sugerties, kurią skatina paviršinių optinių plazmonų rezonansai GaAs nanovielutėse. THz emisijos efektyvumas iš Cu-In chalkogenidų sluoksnių stipriai priklauso nuo jų stechiometrijos ir viršutinio skaidraus kontakto parametrų, ir gali būti naudojamas saulės elementų, pagamintų šių sluoksnių pagrindu, vidinių elektrinių laukų tyrimui.

Šio darbo tikslas buvo susipažinti su terahercinių impulsų generavimo ir detektavimo būdais, įsisavinti įvairias terahercinių impulsų panaudojimo metodikas bei pritaikyti jas puslaidininkių medžiagų ir puslaidininkinių prietaisų tyrimui. Buvo tirtos trys medžiagų grupės: GaAsBi, GaAs nanovielutės ir Cu – In chalkogenidai. Tyrimui buvo naudojamos: THz – TDS, optinio žadinimo – THz zondavimo, optinio žadinimo – optinio zondavimo bei THz sužadinimo spektroskopijos metodikos. Pagrindiniai rezultatai aprašyti disertacijoje yra šie: GaAsBi bandinių atkaitinimas stipriai sumažino krūvininkų gyvavimo trukmes, kas yra naudinga THz komponentų gamyboj. Optinio praskaidrėjimo efektas ir pikosekundžių eilės krūvininkų gyvavimo trukmės GaAsBi epitaksiniuose sluoksniuose su 10% ir daugiau Bi atomų stebimas žadinant juos optine spinduliuote, kurios bangos ilgiai siekia iki 1600 nm. Šios GaAsBi bandinių savybės leidžia juos priakyti įsisotinančių sugėriklių veidrodžių gamyboje. Bandiniai su GaAs nanovielutėmis emituoja THz spinduliuotę kelis kartus geriau nei GaAs padėklas, dėl padidėjusios sugerties, kurią skatina paviršinių optinių plazmonų rezonansai GaAs nanovielutėse. THz emisijos efektyvumas iš Cu-In chalkogenidų sluoksnių stipriai priklauso nuo jų stechiometrijos ir viršutinio skaidraus kontakto parametrų, ir gali būti naudojamas saulės elementų, pagamintų šių sluoksnių pagrindu, vidinių elektrinių laukų tyrimui. / The goal of this dissertation work was to develop pulsed terahertz radiation techniques and use them to study different properties of the semiconductor materials and semiconductor devices. Three groups of materials were investigated: GaAsBi, GaAs nanowires, copper-indium chalcogenide. The used techniques are THz-TDS, optical pump – THZ probe, optical pump – optical probe and THz excitation spectral measurements. The main results that were presented in this dissertation are the following: thermal annealing has resulted in the shortening of electron lifetime in GaAsBi to picosecond values, which is important achievement for the application of this material in THz range components. In GaAsBi layers with larger than 10% Bi content absorption bleaching recovering on the picosecond time scale and its saturation can be realized when the wavelengths of the optical signals are as long as 1600 nm. The results of these studies can be applied in the production of SESAM with bismide absorption layer. The samples with GaAs nanowires emit THz radiation several times better than the bulk GaAs substrates due to enhanced light absorption because of localized surface plasmon resonances in GaAs nanowires. THz emission efficiency from thin copper-indium chalcogenide layers strongly depends on their stoichiometry and on the parameters of the top transparent contact layers, thus it can be used for the mapping of built-in electric fields in solar cells made from these layers.

The doping concentration and resistivity of tin doped Gallium arsenide nanowires (GaAs NWs) have been investigated using Hall effect-, 4-probe-, transmission line-, and field effect measurements. Single nanowires were contacted using electron beam lithography followed by thermal evaporation of Au/Ti (900/100 Å). The Sn precursor (TESn) molar ratios of the investigated nanowires were 8.5·10-7, 1.7·10-6, 3.4·10-6 and 6.8·10-6 resulting in doping concentrations ranging from 4.64·1013 to 2.11·1017 cm-3 and resistivities from ~0.01 to ~1 Ωcm. The yield of the device fabrication was 2.4-7.1 % and evaluation of additional samples should be done in order to establish the validity of the results. The contact material was proved to work well with the higher doped samples but non-ohmic, highly resistive behavior was seen in the lower doped devices. A resistivity gradient along the length of the nanowires was found to be present, most likely the result of a doping gradient. The sample series with TESn molar ratio 1.7·10-6 showed more tapering than the other series possibly leading to a highly doped shell, which was indicated by 4-probe measurements.

Nanomaterials are the heart of nanoscience and nanotechnology. Research into nanostructures has been vastly expanding worldwide and their application spreading into numerous branches of science and technology. The incorporation of these materials in commercial products is revolutionising the current technological market. Nanomaterials have gained such enormous universal attention due to their unusual properties, arising from their size in comparison to their bulk counterparts. These nanosized structures have found applications in major devices currently under development including fuel cells, computer chips, memory devices, solar cells and sensors. Due to their aforementioned importance nanostructures of various materials and structures are being actively produced and investigated by numerous research groups around the world. In order to meet the market needs the commercialisation of nanomaterials requires nanomaterial fabrication mechanisms that will employ cheap, easy and low temperature fabrication methods combined with environmentally friendly technologies. This thesis investigates low temperature growth of various one-dimensional nanostructures for their potential application in chemical sensors. It proposes and demonstrates novel materials that can be applied as catalysts for nanomaterial growth. In the present work, zinc oxide (ZnO) and silicon (Si) based nanostructures have been fabricated using low temperature growth methods including hydrothermal growth for ZnO nanowires and plasma-enhanced chemical vapour deposition (PECVD) technique for Si nanostructures. The structural, optical and electrical properties of these materials have been investigated using various characterisation techniques. After optimising the growth of these nanostructures, gas and biosensors have been fabricated based on Si and ZnO nanostructures respectively in order to demonstrate their potential in chemical sensors. For the first time, in this thesis, a new group of materials have been investigated for the catalytic growth of Si nanostructures. Interesting growth observations have been made and theory of the growth mechanism proposed. The lowest growth temperature in the published literature is also demonstrated for the fabrication of Si nanowires via the PECVD technique. Systematic studies were carried out in order to optimise the growth conditions of ZnO and Si nanostructures for the production of uniformly shaped nanostructures with consistent distribution across the substrate. v The surface structure and distribution of the variously shaped nanostructures has been analysed via scanning electron microscopy. In addition, the crystallinity of these materials has been investigating using Raman and X-ray diffraction spectroscopies and transmission electron microscopy. In addition to the fabrication of these one-dimensional nanomaterials, their potential application in the chemical sensors has been tested via production of a glucose biosensor and an isopropyl alcohol vapour gas sensor based on ZnO and Si nanostructures respectively. The operation of the devices as sensors has been demonstrated and the mechanisms explored.

We report the synthesis of ultra-high aspect ratio copper nanowires (CuNW) and fabrication of CuNW-based transparent conductive electrodes (TCE) with high optical transmittance (> 80%) and excellent sheet resistance (R-s < 30 Omega/sq). These CuNW TCEs are subsequently hybridized with aluminum-doped zinc oxide (AZO) thin-film coatings, or platinum thinfilm coatings, or nickel thin-film coatings. Our hybrid transparent electrodes can replace indium tin oxide (ITO) films in dye-sensitized solar cells (DSSCs) as either anodes or cathodes. We highlight the challenges of integrating bare CuNWs into DSSCs, and demonstrate that hybridization renders the solar cell integrations feasible. The CuNW/AZO-based DSSCs have reasonably good open-circuit voltage (V-oc = 720 mV) and short-circuit current-density (J(sc) = 0.96 mA/cm(2)), which are comparable to what is obtained with an ITO-based DSSC fabricated with a similar process. Our CuNW-Ni based DSSCs exhibit a good open-circuit voltage (V-oc = 782 mV) and a decent short-circuit current (J(sc) = 3.96 mA/cm2), with roughly 1.5% optical-to-electrical conversion efficiency.

The key challenge for a nanomaterial based sensor is how to synthesize in bulk quantity and fabricate an actual device with insightful understanding of operational mechanisms during performance. I report here effective, controllable methods that exploit the concepts of the "green approach" to synthesize two different one-dimensional nanostructures, including tin oxide nanowires and carbon nanotubes. The syntheses are followed by product characterization and sensing device fabrications as well as sensor performance understanding at the molecular level. Sensor-analyte response and recovery kinetics are also presented. The first part of the thesis describes bulk-scale synthesis and characterization of tin oxide nanowires by the molten salt synthetic method and the nanowire doping with antimony (n-types) and lithium. The work builds on the success of using n-doped SnO2 nanoparticles to selectively detect chlorine gas at room temperature. Replacing n-doped nanoparticles with n-doped nanowires reduces the number of inter-particle electron hops between sensing electrodes. The nanowire based sensors show unprecedented 5 ppb detectability of corrosive Cl2 gas concentration in air. At the higher range, 10 ppm of Cl2 gas leads to a 250 fold increase in the device resistance. During sensor recovery, FT-IR studies show that dichlorine monoxide (Cl2O) and chlorine dioxide (ClO2) are the desorbing species. Long term stability of devices is affected by lattice oxygen vacancies replaced by chlorine atoms. Bulk-scale synthesis of multiwall carbon nanotube (MWCNTs) was achieved by a novel inexpensive synthetic method. The green chemistry method uses the non-toxic and easy to handle solid carbon source naphthalene. The synthesis is carried out by simply heating naphthalene and organometallic precursors as catalysts in a sealed glass tube. Synthesis at 610º C leads to MWCNTs of 50 nm diameter and lengths exceeding well over microns. MWCNT doping is attempted with nitrogen (n-type) and boron (p-type) precursors. Palladium nanoparticles decorated on as-synthesized MWCNTs are employed for specific detection of explosive hydrogen gas with concentrations far below the explosive concentration limits. During performance, the sensor exhibits abnormal response behaviors at hydrogen gas concentrations higher than 1%. A model of charge carrier inversion, brought about by reduction of MWCNT by hydrogen molecules dissociated by Pd nanoparticles is proposed.

Doctor of Philosophy / Department of Chemical Engineering / James H. Edgar / The exceptional radiation resistance, high melting point, and wide energy bandgap (3.2 eV) of icosahedral boron arsenide, B[subscript]12As[subscript]2, make it an attractive candidate for applications in radiation intense environments, for example, in radioisotope batteries. These devices have potential lifetimes of decades rather than days or weeks that are typical of conventional chemical power cells. Solid state neutron detectors are another potential application of this semiconductor, as the boron-10 isotope has a high thermal neutron capture cross-section, orders of magnitude higher than most elements. To produce high quality crystalline B[subscript]12As[subscript]2 for these applications, this research focused on the epitaxy and electrical properties of B[subscript]12As[subscript]2 thin films. The major findings include the following. Twin-free heteroepitaxial B[subscript]12As[subscript]2 layers were obtained on m-plane 15R-SiC and c-plane 4H-SiC inclined 4° and 7° off-axis in the [1-100] direction. These substrates exposed asymmetric step-terrace surface structures that force B[subscript]12As[subscript]2 layers to adopt a single orientation, thus, twins were eliminated. Consequently, the crystal quality was greatly improved over films on on-axis c-plane 6H-SiC, yielding a maximum hole mobility of 80 cm[superscript]2V[superscript]-1s[superscript]-1, nearly 100 times higher than previously reported values. B[subscript]12As[subscript]2 epilayers grown at 1300°C had the lowest defect densities, smallest residual strains, highest mobility and highest deposition rate. Excess AsH[subscript]3 concentration was advantageous to prevent the loss of arsenic from the epilayer. Undoped B[subscript]12As[subscript]2 exhibited a variable-range-hopping conduction, indicating it was a highly disordered system. All films were p-type with a room temperature hole concentration on the order of 10[superscript]12~10[superscript]15cm[superscript]-3. The thermal activation energy of acceptors varied from 0.15 eV to 0.33 eV. The Hall mobility was dominated by impurity scattering at low temperatures and by polar phonon scattering at high temperatures. H, C, O and Si were the major impurities present in the undoped B[subscript]12As[subscript]2 films with concentrations on the order of 10[superscript]18~10[superscript]19 cm[superscript]-3. Si doping and annealing decreased the resistivity by up to two orders of magnitude. The density of localized states was small in the undoped B[subscript]12As[subscript]2 as the intrinsic acceptor levels (IALs) were compensated by the boron interstitials. However, in Si-doped B[subscript]12As[subscript]2, Si may prevent the interstitial boron atoms from compensating the IALs, yielding a decreased density of localized states. The Hall mobility of B[subscript]12As[subscript]2 epilayer was significantly reduced with increasing silicon concentration.

In this study, template-based methods are used for the fabrication of various nanostructures such as nandots, nanorods, nanowires, nanotubes, and core-shell structures. Porous alumina membranes were employed as templates and metal nanostructures were synthesized in the templates by electrodeposition. By using lithography techniques, controlled patterned nanostructures were also fabricated on alumina templates. The magnetic properties of the various metal nanostructures were investigated. The pore size, interpore distance, and pore geometry highly affect magnetic properties of nanostructures grown in the templates. Hexagonally ordered porous alumina templates can be fabricated by two-step anodization. The pore diameters and interpore distances were readily controlled by appropriately changing anodization conditions and pore widening time. Alumina templates with various pore geometries were also successfully synthesized by changing applied voltage, increasing and decreasing, during a third anodization step. To understand magnetic properties of nanostructures with different aspect rations in the form of nanodots, nanorods, or nanowires, Fe nanostructures were fabricated in the templates by controlling of electrodeposition times. The coercivity of nanostructures increased with increasing aspect ratio. The anisotropy of the arrays was governed by the shape anisotropy of the magnetic objects with different aspect ratios. nanowires in mild-hard alumina and conventional alumina templates showed distinct differences in the squareness of hysteresis loops and coercivity both as a function of pore structure and magnetic component. Iron oxide nanotubes with a unique inner-surface were also fabricated by an electrodeposition method. β-FeOOH nanotubes were grown in alumina templates and transformed into hematite and magnetite structures during various heating processes. Hematite nanotubes are composed of small nanoparticles less than 20 nm diameters and the hysteresis loops and FC-ZFC curves show superparamagnetic properties without the Morin transition. In the case of magnetite nanotubes, which consist of slightly larger nanoparticles, hysteresis loops show ferromagnetism with weak coercivity at room temperature while FC-ZFC curves exhibit the Verwey transition at 125 K. For the patterning of nanowires, lithography techniques including nanosphere lithography and e-beam lithography were used. Nanosphere lithography used self-assembled PS spheres as a mask creates holes between spheres and the size of the holes is determined by the size and geometry of ordered PS spheres on the templates. This method can grow patterned nanowires arrays and also produce unique cup-shaped nanostructures with sizes ranging from micrometer down to several nanometers. E-beam lithography was also combined with template-based electrodeposition. Of these two lithographic methods, this one is the most powerful in the fabrication of patterned nanostructures with high aspect ratios. Various features and the sizes of patterned structures can be readily controlled. By the directing the pore diameters and interpore distances of the alumina template, the size and number of patterned nanowires are also adjustable.