A novel method of synthesizing and controlling the size of germanium nanocrystals was developed. A tri-layer structure comprising of a thin (~5nm) SiO₂ layer grown using rapid thermal oxidation (RTO), followed by a layer of Ge+SiO₂ of varying thickness (6 - 20 nm) deposited using the radio frequency (r.f.) co-sputtering technique and a SiO₂ cap layer (50nm) deposited using r.f. sputtering, was investigated. It was verified using TEM that germanium nanocrystals of sizes ranging from 6 – 20 nm were successfully fabricated after thermal annealing of the tri-layer structure under suitable conditions. The nanocrystals were found to be well confined by the RTO SiO₂ and the cap SiO₂ under specific annealing conditions. The electrical properties of the tri-layer structure have been characterized using MOS capacitor test devices. A significant hysteresis can be observed from the C-V measurements and this suggests the charge storage capability of the nanocrystals. The proposed technique has the potential for fabricating memory devices with controllable nanocrystals sizes. / Singapore-MIT Alliance (SMA)

The electro-optical properties of the ZnO/Si heterojunction embedded with self-assembled gold nanoparticles on patterned silicon substrate are investigated in this master thesis. High quality n-type ZnO film is deposited on patterned p-type silicon substrate by radio-frequency sputtering to form a ZnO/Si pn junction. The patterned silicon substrates are prepared by ICP-RIE using self-assembled nickel metal dot and silicon dioxide as etching mask. The optimum ICP process conditions of silicon nanopillars are CF4/Ar ~ 40/40 sccm and bias/RF power 400/400 W. Silicon nanopillars of diameter ~ 50 nm and height 100~400 nm are formed on the substrate surface. ZnO film is then deposited of a growth rate ~ 12 nm/min at the substrate temperature = 200oC. The plasmonic effects on the electro-optical properties, including photoluminescence (PL), reflection, and electrical characteristics, are studied by adding self-assembled gold nanoparticles within the ZnO film. The self-assembled gold nanoparticles are formed by thermal deposition and rapid thermal annealing at 700oC. The gold nanoparticles are observed by scanning electron microscopy (SEM) and particles of diameter about 100 nm. The PL intensity of ZnO is enhanced more than ten times at the peak wavelength = 380 nm by adding the gold nanoparticles and silicon nanopillars. Strong blue emission light could be saw with the naked eyes. For the electric characteristics, self-assembled gold nanoparticles in patterned ZnO/Si heterojunction show photoelectric conversion phenomenon because of high electromagnetic absorption and plasmonic effects.

The increasing energy demand, combined with the use of harmful non-renewable energy sources calls for the search of alternative methods to cover our energy need.Renewable energy can be harvested in different ways, through the movement of wind and water, biomass, or directly from the rays of the sun, as in the case of photovoltaic (PV) devices. Whilst crystalline silicon (c-Si) is the most common absorber used for solar cells, other technologies are emerging. Solar cells with copper indium gallium diselenide (CIGS) as an absorber have the possibility of being flexible, which is an advantage due to the many more application possibilities that appear compared to the rigid and heavy c-Si solar cells. CIGS solar cells have some long-term stability issues, especially regarding ingression of atmospheric species through the front contact layer. This calls for further research in the front contact of the CIGS solar cell, exploring alternative materials to prevent degradation. The front contact of a solar cell must be both optically transparent and conduct electricity. Transparent conductive oxides (TCO) are materials characterized by the ability to conduct electricity, while also possessing a certain degree of optical transparency. The combination of conductivity and transparency makes TCOs ideal as front contacts in solar cells. A very common TCO for front contacts in CIGS solar cells is aluminum-doped zinc oxide (AZO) due to its low cost, good electrical conductivity and optical transparency. Because of its low resistance to degradation in humid environments more robust TCO alternatives, such as indium-doped tin oxide (ITO), are being investigated. Indium-doped tin oxide possesses similar electrical and optical properties as AZO, but better stability in humid environments.The ITO was deposited through RF magnetron sputtering, on a glass substrate to be able to measure optical properties. Initially, experiments focusing on oxygen content in the deposition atmosphere were done, together with a reproducibility experiment. This gave useful information about sputtering parameters and stability of the deposition. Thereon, an experiment was done varying three parameters: oxygen content in deposition atmosphere, sputtering power and temperature of substrate. A statistical software was used to analyze the data, identifying the effects of the changing parameters. The best performing samples were made with an oxygen content of 0,4-0,6 vol%. A high sensibility for oxygen in the system was also observed, as a result of the initial reproducibility experiments. This led to the introduction of a sacrificial deposition step after the machine had been shut down. Optimal substrate temperature was around 150°Cand it was not possible to go higher due to sensibility of the underlying solar cell layers.A lower threshold for the film thickness, located somewhere between 125 and 175 nm, was observed. Films with thickness below this threshold experienced a large resistivityincrease. Further depositions with higher oxygen content are advised to see if the properties of the films further improve.

All solid state Li-ion batteries (thin film micro batteries) have become inevitable for miniaturized devices and sensors as power sources. Fabrication of electrode materials for batteries in thin film form has been carried out with the existing technologies used in semiconductor industry. In the present thesis, radio frequency (RF) sputtering has been chosen for deposition of cathode material (ceramic oxides) thin films because of several advantages such as precise thickness control and deposition of compound thin films with equivalent composition. Conventional sputtering involves fabrication of thin film using custom made pellet according to the specification of sputter gun. However several issues such as target breaking are inevitable with the pellet sputtering. To forfend the issues, powder sputtering has been implemented for the deposition of various thin film cathodes in an economically feasible approach. Optimization of various process parameters during film deposition of cathode materials LiCoO2, Li2MnO3, LiNixMnyO4, mixed oxide cathodes of LiMn2O4, LiCoO2 and TiO2 etc., have been executed successfully by the present approach to achieve optimum electrochemical performance. Thereafter the optimized process parameters would be useful for selection of cathode layers for micro battery fabrication. Chapter 1 gives a brief introduction to the Li ion and thin film solid state batteries. It also highlights the advantages of powder sputtering compared to conventional pellet sputtering. In Chapter 2, the materials used and methods employed for the fabrication of thin film electrodes and analytical characterizations have been discussed. In chapter 3, implementation of powder sputtering for the deposition of LiCoO2 thin films has been discussed. X-Ray diffraction (XRD), X-Ray photoelectron spectroscopy (XPS) and electrochemical investigations have been carried out and promising results have been achieved. Charge discharge studies delivered a discharge capacity of 64 µAh µm-1 cm-2 in the first cycle in the potential range 3.0-4.2 V vs. Li/Li+. The possible causes for the moderate cycle life performance have been discussed. Systematic investigations for RF power optimization for the deposition of Li2-xMnO3-y thin films have been carried out. Galvanostatic charge discharge studies delivered a highest discharge capacity of 139 µAh µm-1cm-2 in the potential window 2.0-3.5 V. Thereafter, effect of LMO film thickness on electrochemical performance has been studied in the thickness range 70 nm to 300 nm. Films of lower thickness delivered higher discharge capacity with good cycle life than the thicker films. These details are discussed in chapter 4. In Chapter 5, fabrication and electrochemical performance of LiNixMnyO4 thin films are presented. LMO thin films have been deposited on nickel coated stainless steel substrates. The as deposited films were annealed at 500 °C in ambient conditions. Nickel diffuses in to LMO film and results in LiNixMnyO4 (LMNO) film. These films were further characterized. Electrochemical studies were conducted up to higher potential 4.4 V resulted in discharge capacities of the order of 55 µAh µm-1cm-2. In chapter 6, electrochemical investigations of mixed oxide thin films of LiCoO2 and LiMn2O4 have been carried out. Electrochemical investigations have been carried out in the potential window 2.0–4.3 V and a discharge capacity of 24 µAh µm-1cm-2 has been achieved. In continuation, TiO2 powder was added to the former composition and the deposited films were characterized for electrochemical performance. The potential window as well as the discharge capacity enhanced after TiO2 doping. Electrochemical characterization has been carried out in the potential window 1.4–4.5 V, and a discharge capacity of 135 µAh µm-1cm-2 has been achieved. Finally chapter 7 gives overall conclusions and future directions to the continuation of the work.