This thesis is composed of three projects including the AC magnetic susceptibility study of high-temperature superconductor YBa$_2$Cu$_3$O$_{7-\delta}$, the ionic-liquid gating study of the Mott insulator Sr$_2$IrO$_4$, and the single-electron study of quantum dot device with self-assembled nanocrystal PbS. Chapter 1 covers a general introduction to all three projects. The basic background and the motivation for each project are presented. Project I is covered in Chapter 2, Chapter 3, and Chapter 4. The first part of Chapter 2 is a theoretical introduction to the Bardeen-Cooper-Schrieffer theory of superconductivity with its main conclusions presented. This chapter builds a basis for the use of high pressure technique to YBa$_2$Cu$_3$O$_{7-\delta}$ in the later chapters. The rest of Chapter 2 reviews the work in the study of high-temperature superconductors, especially on YBa$_2$Cu$_3$O$_{7-\delta}$, on both experiments and theories and the possible applications of high-temperature superconductors. Chapter 3 introduces the YBa$_2$Cu$_3$O$_{7-\delta}$ sample preparation process and the characterisation. A dry cryomagnetic equipment was employed for the measurement. The results and the discussion are presented in Chapter 4. Project II is described in Chapter 5, Chapter 6, and Chapter 7. Chapter 5 firstly introduces the background knowledge of the gated material SrTiO$_3$ and the technical details of the ionic-liquid gating technique. Then the sample growth and the characterisation are presented. The fabrication process of Sr$_2$IrO$_4$ and SrTiO$_3$ (material for a control experiment) are described in Chapter 6. Chapter 7 covers the measurement and the result of the fabricated devices and related discussion. Project III ranges from Chapter 8, and Chapter 9. A literature review of quantum-dot devices and self-assembled nanocrystals is presented in Chapter 8. The experimental design of this nanocrystal quantum dot device is also included. Following it, the fabrication process of quantum-dot devices and the techniques used for fabrication are introduced in the start of Chapter 9. Chapter 9 also gives a description of the probe-station for measurements. The results and discussion of the measurements are covered in the last section of Chapter 9. Chapter 10 summarises and concludes the three projects stated above and gives some suggestions about the directions for future work.

A method of synthesizing and controlling the size of germanium nanocrystals is developed. A tri-layer metal-insulator-semiconductor (MIS) memory device structure comprising of a thin (~5nm) silicon dioxide (SiO₂) layer grown using rapid thermal oxidation (RTO), followed by a layer of Ge+SiO₂ of varying thickness (3 - 6 nm) deposited using a radio frequency (rf) co-sputtering technique, and a capping SiO₂ layer (50nm) deposited using rf sputtering is investigated. It was verified that the size of germanium (Ge) nanocrystals in the vertical z-direction in the trilayer memory device was controlled by varying the thickness of the middle (cosputtered Ge+SiO₂) layer. From analyses using transmission electron microscopy and capacitance-voltage measurements, we deduced that both electrons and holes are most likely stored within the nanocrystals in the middle layer of the trilayer structure rather than at the interfaces of the nanocrystals with the oxide matrix. / Singapore-MIT Alliance (SMA)

The effect of germanium (Ge) concentration and the rapid thermal oxide (RTO) layer thickness on the nanocrystal formation and charge storage/retention capability of a trilayer metal-insulator-semiconductor device was studied. We found that the RTO and the capping oxide layers were not totally effective in confining the Ge nanocrystals in the middle layer when a pure Ge middle layer was used for the formation of nanocrystals. From the transmission electron microscopy and secondary ion mass spectroscopy results, a significant diffusion of Ge atoms through the RTO and into the silicon (Si) substrate was observed when the RTO layer thickness was reduced to 2.5 nm. This resulted in no (or very few) nanocrystals formed in the system. For devices with a Ge+SiO₂ co-sputtered middle layer (i.e., lower Ge concentration), a higher charge storage capability was obtained than with devices with a thinner RTO layer, and the charge retention time was found to be less than in devices with a thicker RTO layer. / Singapore-MIT Alliance (SMA)

Silicon as a mono-crystalline bulk semiconductor is today the predominant material in many integrated electronic and photovoltaic applications. This has not been the case in lighting technology, since due to its indirect bandgap nature bulk silicon is an inherently poor light emitter.With the discovery of efficient light emission from silicon nanostructures, great new interest arose and research in this area increased dramatically.However, despite more than two decades of research on silicon nanocrystals and nanowires, not all aspects of their light emission mechanisms and optical properties are well understood, yet.There is great potential for a range of applications, such as light conversion (phosphor substitute), emission (LEDs) and harvesting (solar cells), but for efficient implementation the underlying mechanisms have to be unveiled and understood.Investigation of single quantum emitters enable proper understanding and modeling of the nature and correlation of different optical, electrical and geometric properties.In large numbers, such sets of experiments ensure statistical significance. These two objectives can best be met when a large number of luminescing nanostructures are placed in a pattern that can easily be navigated with different measurement methods.This thesis presents a method for the (optional) simultaneous fabrication of luminescent zero- and one-dimensional silicon nanostructuresand deals with their structural and optical characterization.Nanometer-sized silicon walls are defined by electron beam lithography and plasma etching. Subsequent oxidation in the self-limiting regime reduces the size of the silicon core unevenly and passivates it with a thermal oxide layer.Depending on the oxidation time, nanowires, quantum dots or a mixture of both types of structures can be created.While electron microscopy yields structural information, different photoluminescence measurements, such as time-integrated and time-resolved imaging, spectral imaging, lifetime measurements and absorption and emission polarization measurements, are used to gain knowledge about optical properties and light emission mechanisms in single silicon nanocrystals.The fabrication method used in this thesis yields a large number of spatially separated luminescing quantum dots randomly distributed along a line, or a slightly smaller number that can be placed at well-defined coordinates. Single dot measurements can be performed even with an optical microscope and the pattern, in which the nanostructures are arranged, enables the experimenter to easily find the same individual dot in different measurements.Spectral measurements on the single dot level reveal information about processes that are involved in the photoluminescence of silicon nanoparticles and yield proof for the atomic-like quantized nature of energy levels in the conduction and valence band, as evidenced by narrow luminescence lines (~500 µeV) at low temperature. Analysis of the blinking sheds light on the charging mechanisms of oxide-capped Si-QDs and, by exposing exponential on- and off-time distributions instead of the frequently observed power law distributions, argues in favor of the absence of statistical aging. Experiments probing the emission intensity as a function of excitation power suggest that saturation is not achieved. Both absorption and emission of silicon nanocrystals contained in a one-dimensional silicon dioxide matrix are polarized to a high degree. Many of the results obtained in this work seem to strengthen the arguments that oxide-capped silicon quantum dots have universal properties, independently of the fabrication method, and that the greatest differences between individual nanocrystals are indeed caused by individual factors like local environment, shape and size (among others). / <p>QC 20120920</p>

Solar energy harvesting demands low-cost energy conversion in the infrared from 1 – 2 μm. However, solution-processed photovoltaic devices have remained relatively inefficient in this spectral region. Herein, lead sulfide colloidal nanocrystal quantum dots are used to facilitate efficient infrared power conversion. Solution-cast nanocrystal films are employed in a simple metal/semiconductor/metal architecture to produce a photovoltaic effect. It is shown that a Schottky barrier is induced, which is responsible for the charge separating action. Through optimization of chemical processes and device fabrication, the photovoltaic response is maximized. The infrared power conversion efficiency reaches 4.2%, which sets a new precedent for solution-processed photovoltaic cells. Furthermore, the devices exhibit efficient broadband solar power conversion and show promise for multijunction cell architectures. Carrier drift through a large depletion region near the Schottky contact is determined to be the dominant transport mechanism.

In large molecular systems such as DNA, supramolecular complexes and dendrimers, functional groups located at different parts of the molecular structure can act as charge donors or acceptors, and photoinduced intramolecular charge transfer can occur. An analogous scenario can be found in colloidal semiconductor nanocrystals, most evident in type-II heterostructures, where the relative band-alignment of the constituent materials are in a stagger configuration. Such a configuration, provides an energetically favourable situation for an photo-generated electron to be transferred from one material to the other, confining the electron and the hole in different domains of the nanostructure. A less obvious scenario in nanocrystals is when the core is thought of as the donor group, and the surface as the acceptor group. In such a scenario, the localization of electron or hole at surface defect sites, a process that occurs in every nanocrystal, can be thought of as an ``intramolecular" charge transfer. The studies presented in this dissertation are an attempt to further understand charge transfer processes in semiconductor nanostructures, in particular, those occurring within the same nanocrystals. This is carried out by a combination of spectroscopic techniques and modelling. First, time-resolved fluorescence measurements are used to investigated surface trapping/de-trapping dynamics in CdSe and CdSe/CdS/ZnS core/shell/shell quantum dots. A kinetic model, in which trapping/de-trapping is described with Marcus' classical electron transfer theory, is used to analyzed our results, yielding excellent agreement between model and experiment. Second, the influence of temperature and solvent environment in the optical spectra of CdSe/CdTe nanorods are examined. Solvatochromic shifts in these heterostructures are found to be larger than those observed in core-only quantum dots. Finally, ultrafast dynamics and biexciton states in CdSe/CdTe quantum dots are probed using two-dimensional optical spectroscopy. The fine structure of the lowest exciton and biexciton states are calculated for a model system with type-II band-alignment and simulations of 2D spectra are performed.

Solar energy harvesting demands low-cost energy conversion in the infrared from 1 – 2 μm. However, solution-processed photovoltaic devices have remained relatively inefficient in this spectral region. Herein, lead sulfide colloidal nanocrystal quantum dots are used to facilitate efficient infrared power conversion. Solution-cast nanocrystal films are employed in a simple metal/semiconductor/metal architecture to produce a photovoltaic effect. It is shown that a Schottky barrier is induced, which is responsible for the charge separating action. Through optimization of chemical processes and device fabrication, the photovoltaic response is maximized. The infrared power conversion efficiency reaches 4.2%, which sets a new precedent for solution-processed photovoltaic cells. Furthermore, the devices exhibit efficient broadband solar power conversion and show promise for multijunction cell architectures. Carrier drift through a large depletion region near the Schottky contact is determined to be the dominant transport mechanism.

In large molecular systems such as DNA, supramolecular complexes and dendrimers, functional groups located at different parts of the molecular structure can act as charge donors or acceptors, and photoinduced intramolecular charge transfer can occur. An analogous scenario can be found in colloidal semiconductor nanocrystals, most evident in type-II heterostructures, where the relative band-alignment of the constituent materials are in a stagger configuration. Such a configuration, provides an energetically favourable situation for an photo-generated electron to be transferred from one material to the other, confining the electron and the hole in different domains of the nanostructure. A less obvious scenario in nanocrystals is when the core is thought of as the donor group, and the surface as the acceptor group. In such a scenario, the localization of electron or hole at surface defect sites, a process that occurs in every nanocrystal, can be thought of as an ``intramolecular" charge transfer. The studies presented in this dissertation are an attempt to further understand charge transfer processes in semiconductor nanostructures, in particular, those occurring within the same nanocrystals. This is carried out by a combination of spectroscopic techniques and modelling. First, time-resolved fluorescence measurements are used to investigated surface trapping/de-trapping dynamics in CdSe and CdSe/CdS/ZnS core/shell/shell quantum dots. A kinetic model, in which trapping/de-trapping is described with Marcus' classical electron transfer theory, is used to analyzed our results, yielding excellent agreement between model and experiment. Second, the influence of temperature and solvent environment in the optical spectra of CdSe/CdTe nanorods are examined. Solvatochromic shifts in these heterostructures are found to be larger than those observed in core-only quantum dots. Finally, ultrafast dynamics and biexciton states in CdSe/CdTe quantum dots are probed using two-dimensional optical spectroscopy. The fine structure of the lowest exciton and biexciton states are calculated for a model system with type-II band-alignment and simulations of 2D spectra are performed.

In developing countries many industries use dyes to colour their products, such as textiles, rubber, paper, cosmetics, leather, plastics, and food industries. Such a wide range of using dyes in many industries increases the demand of dye, and currently 100,000 dyes are commercially available with a rough estimated production of 10⁶ tones/year. Without proper treatment, dye effluent can be mixed with surface and ground water system and it may finally enter the drinking water system. Therefore, the treatment of dye effluents before discharge to the environment has become an global challenge due to the stability and adverse effects of dyes. Among the present methods, adsorption has been preferred to other conventional techniques due to the simple design and operation, low initial investment,effectiveness and insensitivity to toxic substances. The high surface area and the presence of permanent negative charge on the surface makes cellulose nanocrystal (CNC) an excellent candidate for the adsorption of basic (cationic) dyes. The objective of this project is to evaluate the adsorption properties of CNC for the removal of methylene blue from aqueous solution by changing the parameters, such as adsorbent dosage, initial dye concentration, pH, temperature and salt concentration. It was found that the adsorption is independent of pH, however increase in temperature and ionic strength decreased the removal percentage slightly. The Langmuir and Freundlich isotherms were used to evaluate the feasibility of the adsorption process. The adsorption capacity of CNC was determined using the linearized form of Langmuir model. It possessed a value of 118 mg/g at pH 9 and 25 °C. To enhance the adsorption, CNC was oxidized with TEMPO reagent to convert primary hydroxyl groups to carboxyl groups that provides more negative charge. After the oxidation, the adsorption capacity increased from 118 to 769 mg/g.

In developing countries many industries use dyes to colour their products, such as textiles, rubber, paper, cosmetics, leather, plastics, and food industries. Such a wide range of using dyes in many industries increases the demand of dye, and currently 100,000 dyes are commercially available with a rough estimated production of 10⁶ tones/year. Without proper treatment, dye effluent can be mixed with surface and ground water system and it may finally enter the drinking water system. Therefore, the treatment of dye effluents before discharge to the environment has become an global challenge due to the stability and adverse effects of dyes. Among the present methods, adsorption has been preferred to other conventional techniques due to the simple design and operation, low initial investment,effectiveness and insensitivity to toxic substances. The high surface area and the presence of permanent negative charge on the surface makes cellulose nanocrystal (CNC) an excellent candidate for the adsorption of basic (cationic) dyes. The objective of this project is to evaluate the adsorption properties of CNC for the removal of methylene blue from aqueous solution by changing the parameters, such as adsorbent dosage, initial dye concentration, pH, temperature and salt concentration. It was found that the adsorption is independent of pH, however increase in temperature and ionic strength decreased the removal percentage slightly. The Langmuir and Freundlich isotherms were used to evaluate the feasibility of the adsorption process. The adsorption capacity of CNC was determined using the linearized form of Langmuir model. It possessed a value of 118 mg/g at pH 9 and 25 °C. To enhance the adsorption, CNC was oxidized with TEMPO reagent to convert primary hydroxyl groups to carboxyl groups that provides more negative charge. After the oxidation, the adsorption capacity increased from 118 to 769 mg/g.