xiii, 84 p. ; ill. / This dissertation describes the deposition and characterization of an amorphous thin film with a composition near that of CuInSe 2 (CIS). The creation of an amorphous intermediate leads to a crystalline film at low annealing temperatures. Thin films were deposited from elemental sources in a custom built high vacuum chamber. Copper-selenium and indium-selenium binary layered samples were investigated to identify interfacial reactions that would form undesired binary intermediate compounds resulting in the need for high temperature annealing. Although the indium-selenium system did not form interfacial compounds on deposit, indium crystallized when the indium layer thickness exceeded 15 angstroms, disrupting the continuity of the elemental layers. Copper-selenium elemental layers with a repeat thickness of over 30 angstroms or compositions with less than 63% selenium formed CuSe on deposit. Several deposition schemes were investigated to identify the proper deposition pattern and thicknesses to form the CIS amorphous film. Simple co-deposition resulted in the nucleation of CIS. A simple stacking of the three elements in the older Se-In-Cu at a repeat thickness of 60 angstroms resulted in the nucleation of CuSe and sometimes CIS. The CIS most likely formed due to the disruption of the elemental layers by the growth of the CuSe. Reduction of the repeat thickness to 20 angstroms eliminated the nucleation of CuSe, as predicted by the study of the binary Cu-Se layered samples, but resulted in the nucleation of CIS, similar to the co-deposited samples. To eliminate both the thick Cu-Se region, and prevent the intermixing of all three elements, a more complex deposition pattern was initiated. The copper and selenium repeat thicknesses were reduced into a Se-Cu-Se-Cu-Se pattern followed by deposition of the indium layer at a total repeat thickness of 60 angstroms. At a Se:Cu ratio of 2:1 and the small repeat thickness, no Cu-Se phases nucleated. Additionally, the Cu-In interface was eliminated. For this deposition scheme, films with a selenium rich composition relative to CuInSez were generally amorphous. Those that were Cu-In rich always nucleated CIS on deposit. Annealing of all samples produced crystalline CIS. / Adviser: David C. Johnson

Research into renewable energy sources is crucially increasing to counteract the ever more concerning impact of non-renewable sources. Theoretically, Quantum Dot Solar Cells (QDSCs) can achieve much greater efficiencies than current, commercial solar cells, but its expansion is still in its very early stages of scientific study and development. In this project TiO2, one of the most efficient and cost-effective photocatalysts, is coupled with Cadmium Selenide (CdSe) Quantum Dots (QD) in a study of interfacial charge transfers. Thus far, in other studies, CdSe QDs have shown some of the most promising results of QDSCs. EPR spectroscopy has been used here to study charge transfer processes in CdSe quantum dot (QD) sensitised titania. Visible light excitation of QDs directly adsorbed onto titania surfaces causes electron transfer to the titania, producing characteristic EPR signals of trapped electrons in the titania. Under ultraviolet excitation the trapped electron signals seen in titania alone are suppressed in the presence of directly adsorbed quantum dots, as is the formation of superoxide in the presence of oxygen. These observations suggest that reverse electron transfer from the titania to the QDs can also occur. No visible light excited electron transfer occurs in the case of QDs attached to the titania surface via bi-linker molecules, but under ultraviolet excitation a similar suppression of electron trapping in the titania phase is seen. These results show that the nature of the interface between the QDs and the titania phase is crucially important in the electron transfer processes in both directions. The study also looks at the pitfalls of synthesis techniques used for making the CdSe QDs as well as the method of attaching it to the TiO2. Ionic deposition, which generally resulted in the best photocurrents in other studies, was discovered early on this project produced very impure samples. Direct Adsorption produces low titania surface coverage, which can potentially be improved. Whereas the lack of discussion in literature of clear purification methods in synthesis techniques for attaching QDs via a bi-linker molecule, through ligand exchange, causes a significant drawback in the study of such systems.

abstract: The energy band gap of a semiconductor material critically influences the operating wavelength of an optoelectronic device. Realization of any desired band gap, or even spatially graded band gaps, is important for applications such as lasers, light-emitting diodes (LEDs), solar cells, and detectors. Compared to thin films, nanowires offer greater flexibility for achieving a variety of alloy compositions. Furthermore, the nanowire geometry permits simultaneous incorporation of a wide range of compositions on a single substrate. Such controllable alloy composition variation can be realized either within an individual nanowire or between distinct nanowires across a substrate. This dissertation explores the control of spatial composition variation in ternary alloy nanowires. Nanowires were grown by the vapor-liquid-solid (VLS) mechanism using chemical vapor deposition (CVD). The gas-phase supersaturation was considered in order to optimize the deposition morphology. Composition and structure were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive x-ray spectroscopy (EDS), and x-ray diffraction (XRD). Optical properties were investigated through photoluminescence (PL) measurements. The chalcogenides selected as alloy endpoints were lead sulfide (PbS), cadmium sulfide (CdS), and cadmium selenide (CdSe). Three growth modes of PbS were identified, which included contributions from spontaneously generated catalyst. The resulting wires were found capable of lasing with wavelengths over 4000 nm, representing the longest known wavelength from a sub-wavelength wire. For CdxPb1-xS nanowires, it was established that the cooling process significantly affects the alloy composition and structure. Quenching was critical to retain metastable alloys with x up to 0.14, representing a new composition in nanowire form. Alternatively, gradual cooling caused phase segregation, which created heterostructures with light emission in both the visible and mid-infrared regimes. The CdSSe alloy system was fully explored for spatial composition variation. CdSxSe1-x nanowires were grown with composition variation across the substrate. Subsequent contact printing preserved the designed composition gradient and led to the demonstration of a variable wavelength photodetector device. CdSSe axial heterostructure nanowires were also achieved. The growth process involved many variables, including a deliberate and controllable change in substrate temperature. As a result, both red and green light emission was detected from single nanowires. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2012

Dans cette thèse, deux semi-conducteurs en séléniure ayant d'excellentes propriétés ont été étudiés afin de développer des matériaux performants pour des applications photoélectriques. Tout d'abord, les nanorodes de Sb2Se3 ont été synthétisés en utilisant une méthode d'injection à chaud, et le plus grand défi associé à la faible conductivité de Sb2Se3 a été relevé en formant des hétérojonctions et/ou par un dopage. Les nanorodes de Sb2Se3 à conductivité électrique nettement améliorée ont été utilisés pour fabriquer des photo-détecteurs prototypes, qui présentent un grand potentiel d'application grâce à leur grande efficacité. Le Sb2Se3 dopés au Sn a été préparé en utilisant un procédé de fusion à haute température. Avec l'augmentation de la concentration en Sn, les cristaux (SnxSb1-x)2Se3 présentent également une grande amélioration de la conductivité et des propriétés photoconductrices. Quatre cibles à base de Sb2Se3 avec la composition chimique de Sb2Se3, Sb2Se3.3, (Sn0.1Sb0.9)2Se3 et Sb2(Se0.9I0.1)3 ont été préparées et les couches minces ont été déposées en utilisant la pulvérisation cathodique. Une étude systématique de la cristallinité, de la morphologie de surface, des propriétés optiques, du type de conduction (p ou n) et des performances photo-électro-chimique des couches minces a été réalisée. Une nouvelle cellule solaire à couches minces de Sb2Se3 avec une quasi-homojonction a été fabriquée pour la première fois et le rendement de conversion atteint déjà un taux très intéressant de 2,65%. Une méthode efficace d'injection à chaud a également été développée pour la synthèse de nano-fleurs uniformes de γ-In2Se3. Une photodiode à hétérojonction formée en déposant une couche mince de nanoflower γ-In2Se3, du type p, sur un substrat en Si de type n, a été fabriquée pour la première fois. Il a été démontré que ce photo-détecteur peut être auto-alimenté avec d'excellentes performances, notamment une réponse rapide et une sensibilité à large bande. / In this dissertation, two different selenide semiconductors with excellent properties have been studied in order to develop high performance materials and devices for photoelectric applications. Firstly, Sb2Se3 nanorods were synthesized via hot-injection method, and the biggest challenge of low conductivity of Sb2Se3 nanorods has been overcome successfully by forming heterojunction and/or doping. The Sb2Se3 nanorods with enhanced electrical conductivity were used for fabricating prototype photodetectors, which show great application potential as highly efficient photodetectors. The Sn-doped Sb2Se3 crystals were successfully prepared by using high-temperature melting process. With increasing Sn doping concentration, the (SnxSb1-x)2Se3 crystals also exhibit a great improvement of conductivity and photoconductive properties. Four Sb2Se3-based targets with the chemical composition of Sb2Se3, Sb2Se3.3, (Sn0.1Sb0.9)2Se3 and Sb2(Se0.9I0.1)3 have been successfully prepared by using high-temperature melting technique. Then thin films have been deposited by using RF magnetron-assisted sputtering. A systematic investigation of the crystallinity, surface morphology, optical properties, p/n type and photo-electro-chemical performance of the thin films has been performed. A novel quasi-homojunction Sb2Se3 thin film solar cells was fabricated for the first time and the highest conversion efficiency obtained in our work reaches already a highly interesting 2.65%. An effective hot-injection method has also been developed for synthesizing uniform γ-In2Se3 nanoflowers. An efficient heterojunction photodiode formed by n-type Si substrate and p-type γ-In2Se3 nanoflower film was fabricated for the first time. It has been demonstrated that this photodetector can be self-powered with excellent performance including fast response and broadband sensibility.

Investigations have been done as of why dust particles appear in a circular pattern on the backside of solar cells produced in sputtering chambers at Midsummer AB. An experimental approach was conducted, where solar cells were produced at standard conditions and their backside studied by material analytical methods. The solar cells dust particles were analyzed by energy-dispersive x-ray spectroscopy and x-ray diffraction, deducing that they consisted of iron selenide (Fe0.89Se). Furthermore, the dust particles appear due to formation of a thin iron selenide film that cracks and delaminate upon cooling from process temperature to room temperature. Iron selenide film thickness was found by energy-dispersive x-ray spectroscopy to occur in a pattern with radial symmetry with respect to the cell center, correlating with the film delamination pattern. The reason to the film formation was due to selenium reacting with the substrate steel at high temperatures (>400 ◦C) in deposition chambers having a selenium environment. The film delamination occurs at a critical film thickness at which stresses in the film is high enough for the film to yield and fracture. It was concluded that iron selenide film formation or delamination must be minimized in order to control dust particle formation. These two phenomena can be mitigated by protective substrate films, change of substrate material, selenium environment optimization or temperature profile optimization and should be researched further to find the most effective and viable solution.

We report on the fundamental properties and device applications of semiconductor nanoparticles. ZnO nanowires and CdSe quantum dots were used, prepared, characterized, and assembled into novel light-emitting diodes and solar cells. ZnO nanowire films were grown electrochemically using aqueous soluble chloride-based electrolytes as precursors at temperatures below 90° C. Dopants were added to the electrolyte in the form of chloride compounds, which are AlCl3, CoCl2, CuCl2, and MnCl2. The optical, magnetic, and structural properties of undoped and transition-metal-ion doped ZnO nanowires were explored. Our results indicate that the as-grown nanowire structures have considerable internal strain, resulting in clearly visible lattice distortions in bright and dark-field transmission electron micrographs. Photo and electroluminescence studies indicate that the strain-induced defects strongly dominate any dopant-related effects. However, annealing at moderate temperature as well as laser annealing induces strain relaxation and leads to dopant activation. Hence, the optical and electrical properties of the nanowires significantly improve, allowing these nanowires to become feasible for use in the fabrication of solar cell and LED devices. In addition, the magnetic impurities incorporated into our ZnO nanowires show superparamagnetic behavior at room-temperature, while Al-doped and undoped ZnO nanowires show no magnetic behavior. The electroluminescence (EL) is achieved from a vertical hybrid p-n junction LED arrangement consisting of a hole-conducting polymer and n-type ZnO nanowires, our group was the first to report this vertical nanowire-based LED in Könenkamp et al., 2004 [12]. The observed EL spectra show an ultraviolet excitonic emission peak and a broad defect-related emission band in the visible range. After annealing at 380° C, the defect related EL peak exhibits a characteristic shift to higher wavelengths, where the magnitude of the shift is dependent on the dopant type. Aluminum incorporation exhibited the most improved exciton related-emission, leading to the emergence of a narrow excitonic luminescence peak around 390 nm, which is close to the bandgap of ZnO. The comparison of spectra obtained from temperature-dependent photoluminescence (PL) measurements, before and after thermal annealing, also indicates that the optical activity of impurities changes noticeably upon annealing. The internal quantum efficiency for PL is measured to be as high as 16 percent for Al-doped samples annealed at 380° C. The PL measurements also show that the excitonic luminescence is preferentially guided, while the defect related emission is more isotropically emitted. The nanostructured heterojunction solar cell is designed such that thin CdSe quantum dot films are embedded between a ZnO nanowire film and a hole-conducting polymer layer. This arrangement allows for enhanced light absorption and an efficient collection of photogenerated carriers. Here, we present a detailed analysis of the pyridine solution and 1,2- ethanedithiol ligand exchange processes of the quantum dots, deposition processes of this quantum dot layer, the conformality of this layer on deeply nanostructured samples, and the effect of a surfactant-aided thermal annealing process. Annealing creates a structural conversion of the quantum dot layers into an extremely thin continuous poly-crystalline film, with typical grain diameters of 30-50 nm. This transition is accompanied by a loss of quantum confinement and a significant improvement of the charge transport in the CdSe layer. The combination of the solution and ligand exchange of CdSe quantum dots, as well as the deposition and optimized annealing processes of this quantum dot layer, resulted in solar cells with an open-circuit voltage up to 0.6 V, a short circuit current of ~15 mA/cm2, an external quantum efficiency of 70 percent, and an energy conversion efficiency of 3.4 percent. This 3.4 percent efficiency is presently one of the best efficiencies obtained for this type of device.

M. Tech. (Department of Biotechnology, Faculty of Applied and Computer Sciences) Vaal University of Technology. / Chemical precipitation method is the most widely used of all methods for preparing good quality semiconductor nanoparticles. Several conditions are optimized for producing the desired size and shape of particles. The parameters such as capping molecule, precursor concentration, time and temperature were investigated using the colloidal hot injection method. The effect of capping agent was the first parameter investigated in the synthesis of copper selenide, copper sulphide and copper oxide nanoparticles. The capping agents of interest in this study were oleylamine (OLA) and trioctylphosphine (TOP), due to their ability to act as reducing agents, surfactant, solvent and enhancement of colloidal stabilization. The use of oleylamine and trioctylphosphine were carried out at 220 °C for 30 minutes. The optical and structural properties of the yielded nanoparticles were characterize using UV/Vis spectroscopy, TEM and XRD and showed dependence on the type capping interactions from the two agents. Nanoparticles synthesized using TOP produced two phases whereas a single phase was observed from OLA as confirmed by XRD. OLA produced bigger particle sizes compared to TOP but with a wider variety of shapes. The wide variety of particle structures of OLA capped nanoparticles was advantageous since different types of bacteria were targeted in this work. Therefore, other synthetic parameters were investigated using OLA as both solvent and capping molecule. Precursor concentration ratio showed bigger effect in the size, and shape of the yielded nanoparticles. For copper selenide and copper sulphide (Cu: Se/ S), 1:1 concentration ratio gave the best optical and structural properties while copper oxide (CuO) nanoparticles demonstrated its best optical and structural properties in 2:1 ratio (Cu: O). Nonetheless, 1:1 precursor concentration ratio was used to optimise other parameters. Since reaction time has a profound effect on the nanocrystals size and shapes, the effect of reaction time in OLA was also investigated. The reaction time showed no effect on the phase composition of the synthesized copper sulphide, copper oxide and copper selenide nanoparticles. Reaction time of 30 minutes gave the best optical (the shape of the absorption band edge and emission maxima values) and structural (size distribution of particles) properties for CuSe and CuS compared to other reaction times (15 min, 45 and 60 min). 15 min reaction time gave the best optical and structural properties for copper oxide but nonetheless, 30 min was used as the optimum reaction time for further optimization. Temperature showed an effect in size, shape and the stoichiometry of the reaction. These effects were confirmed by the optical and structural properties of the synthesized nanoparticles. XRD patterns revealed some differences with the temperature change, indicating an effect on the phase composition of CuS and CuO but not on CuSe nanoparticles. CuSe and CuS nanoparticles synthesized at 220 °C gave the ideal optical and morphological features compared to other temperatures that were selected (160 ºC, 190 ºC and 240 ºC). Nonetheless, CuO revealed its best optical and structural properties at 160 ºC. 220 ºC was deduced to be the optimum temperature for the synthesis of these three materials under the synthetic conditions. The optimum parameter (220 ºC, 30 min and 1:1 ratio) were used to synthesize the three copper chalcogenides which were then tested against Gram-negative (E. coli and P. aeruginosa), Gram-positive (S. aureus and E. faecalis), and fungi (C. albicans). The plant species, Combretum molle and Acacia mearnsii were phytochemical screened for the presence of active organic compounds and the content of total phenols, flavonoids and antioxidants using different solvents. Both C. molle and A. mearnsii revealed the highest phenolic content in acetone extracts. C. molle revealed its highest flavonoid content in methanol extract and its highest free radical scavenging activity in acetone extract. Acetone extracts demonstrated the highest flavonoid content as well as the highest free radical scavenging activity of A. meansii. The solubility of copper chalcogenides and plant extract was tested in four different solvents and the solvent that demonstrated highest solubility was used for the coordination of the plant extract and copper chalcogenides. The plant extract coordinated nanoparticles were tested for their antibacterial and antifungal activity. Their results were compared to those of the active ingredient in their respective solvents from the medicinal plants as well as those of copper chalcogenides nanoparticles without plant extracts using diffusion disk and MICs methods. The synthesized nanoparticles showed better performance than plant extracts with copper oxide performing the best, followed by copper selenide and lastly by copper sulfide. The performance of plants extracts highly dependent on the solvent of extract with acetone showing the best performance for both C. molle and A. Mearnsii followed by ethanol. The addition of active ingredients from C. molle and A. mearnsii to the synthesized nanoparticles did not enhance the performance of these nanoparticles.

The development of digital technology permits the storage and processing of binary data at high rates, with high precision and density. Therefore, over the past few decades, Moore's law has pushed the development of scaling semiconductor devices for computing hardware. Although the current downward scaling trend has reached its scaling limits, a new "More-than-Moore" (MtM) trend has been emphasized as a diversified function of data collection, storage units, and processing devices. The function diversification defined in MtM can be viewed as an alternative form of "scaling down" for electronic systems, as it incorporates non-computing functions into digital ones, allowing digital devices to interact directly with the environment around them. Two-dimensional (2D) materials display promising potential for combining optical sensing and data storage with broadband photoresponse, outstanding photoresponsivity, rapid switching speed, multi-bit data storage, and high energy efficiency. In this work, in-solution 2D materials flakes (Hafnium Diselenide (HfSe2) and Germanium Selenide (GeSe) have been studied as a charge-trapping layer in non-volatile memory through the seamless fabrication process. Furthermore, the behavior of fabricated non-volatile memories under light illumination has been investigated towards in-memory light sensing. Atomic Force Microscopy, RAMAN spectroscopy, and X-ray Diffraction Spectroscopy characterized the charge-trapping materials. The electrical characterization of Metal Oxide Semiconductor (MOS) Capacitor memory revealed a memory window of 4V for the HfSe2 device under ±10V biasing. Intriguingly, the GeSe device exhibited an extraordinarily wide memory window of 11V under the same electrical biasing. Furthermore, the memory endurance for both materials as charge trapping layer (CTL) exceeds the standard threshold of electrical programming and erasing cycles. The accelerated retention test at different temperatures showed the memory device's stability and reliability for both materials. Under light stimuli with electrical readout voltage, the MOS memory exhibited wavelength and intensity-responsive behavior. The MOS memory of HfSe2 has demonstrated remarkable capabilities in storing the detected light signal, while also exhibiting a noteworthy increase in the memory window of approximately 1.8 V when subjected to a laser wavelength of 405 nm. Meanwhile, the GeSe device's CV measurement revealed a similar trend with the greatest memory window enhancements occurring in relation to 465 nm laser wavelength. Under ±6 V biasing in the absence of light, the memory window was found to be 8.3 V. However, following exposure to a 465 nm laser, this value increased significantly to 9.9 V, representing an increment of 1.6 V. In addition, both devices exhibited distinct sensing of various light intensities and an enhanced memory window as a result of the observable Vt shift caused by altering the levels of illumination. This memory enhancement suggests that photoexcited carriers in the CTL layer were responsible for the optical memory behavior. The 2D materials as CTL pave the way for a reconfigurable optical memory with multilevel optical data storage capacity. This research represents a significant step towards the development of a new generation of memory devices that can store and retrieve data using light signals.

Quantum dots are semiconductive particles whose properties are highly influenced by the presence of at least one electron. Cadmium selenide quantum dots were synthesized via colloidal synthesis. Contrary to previous preparations, more focus was placed on the temperature rather than the duration of time at which they form. A series of colored solutions were obtained because the excited quantum dots of various sizes emitted specific wavelengths of light. The emission spectra showed that the temperature-dependent quantum dots were successfully synthesized. The quantum dots were also immobilized on various surfaces, and the luminescence properties were examined. The quantum dots that were immobilized in sol-gels through chemiluminescence (CL) analyses were found to be stable and were able to maintain their luminescence properties with extensive uses and long-term storage. Linear calibration curves were obtained for concentrations of hydrogen peroxide from 1.75 x 10-4 M to 1.75 x 10-2 M in TCPO-CL.

With the advent of the 21st century, one of the serious problems facing mankind is harmful effects of global warming. Add to that the ever increasing cost of fuel and the importance of development of clean energy resources as alternative to fossil fuel has becomes one of the prime and pressing challenges for modern science and technology in the 21st century. Recent studies have shown that energy related sources account for 50% of the total emission of carbon dioxide in the atmosphere. All research activities are focused on developing various technologies that are capable of converting sunlight into electricity with high efficiency and can be produced using a cost-effective process. One of such technologies is the CuIn1-xGaxSe2 (CIGS) and its alloys that can be produced using cost-effective techniques and also exhibit high photo-conversion efficiency. The work presented here discusses some of the fundamental issues related to high volume production of CIGS thin film solar cells. Three principal issues that have been addressed in this work are effect of reduction in absorber thickness on device performance, micrononuniformity involved with amount of sodium and its effect on device performance and lastly the effect of working distance on the properties of molybdenum back contact. An effort has been made to understand the effect of absorber thickness on PV parameters and optimize the process parameters accordingly. Very thin (