Titanium dioxide, TiO2, has potential applications as a photoelectrode for photoelectrochemical generation of hydrogen by splitting water using solar energy and as a photocatalyst for water purification. This study is part of the UNSW research program to process TiO2-based oxide semiconductors as high-performance photoelectrodes and photocatalysts. This study investigates the effect of defect disorder on semiconducting properties of polycrystalline TiO2. This study involved the processing of high-purity polycrystalline TiO2 and determination of its semiconducting properties through measurement of electrical conductivity and thermoelectric power at elevated temperatures (1073-1323K) in controlled oxygen activities [1x10-13 Pa < p(O2) < 75 kPa]. The study included two types of experiments: Determination of electrical properties under conditions of gas/solid equilibrium. The data obtained was used to derive defect disorder and related semiconducting properties Monitoring of electrical properties during equilibration. This data was used to determine the chemical diffusion coefficient. The data obtained under equilibrium conditions indicates that oxygen may be used as a dopant to impose controlled semiconducting properties. In reduced conditions TiO2 is an n-type semiconductor and under oxidizing conditions TiO2 is a p-type semiconductor. The n-type behaviour is associated with oxygen vacancies as the predominant defects and titanium interstitials as the minority defects. The p-type behaviour is closely related to titanium vacancies that are formed during prolonged oxidation. Charge transport at elevated temperature was shown to involve substantial contribution from ions. Analysis of electrical properties enabled determination of several defect-related quantities including the activation enthalpy for oxygen vacancy formation, and the activation energy of the electrical conductivity components related to electrons, holes and ions. The kinetic data obtained during gas/solid equilibration enabled determination of the chemical diffusion coefficient which exhibited a complex dependence on nonstoichiometry. In addition, prolonged oxidation showed that equilibration occurred in two kinetic regimes. One for highly mobile oxygen vacancies and titanium interstitials which quickly reached an ??operational equilibrium?? within hours and another slow kinetic regime for equilibration of titanium vacancies over many thousand hours. The determined chemical diffusion coefficient data may be used to select the processing conditions required to impose uniform concentration of defects within a TiO2.

Thesis (M.S.)--Ohio University, November, 2003. / Title from PDF t.p. Includes bibliographical references (leaves 58-62).

Thesis (M.S.)--Rochester Institute of Technology, 1989. / "References": leaves 20-23.

M.Sc. / Thin film solar cells based on polycrystalline indium diselenide (CulnSe₂) and amorphous silicon (a-Si:H) are promising candidates for the efficient conversion of sunlight into useable, cheap electrical energy. However, typical device structures are rather complex and consists of semiconductor/metal contacts as well as complicated p - n and p - i - n heterojunctions. In this study, CulnSe₂ absorber layers with excellent material properties were prepared by the selenization of metallic alloys. The a-Si:H thin films were deposited by radio frequency (RF) glow discharge in vacuum. The polycrystalline and amorphous absorber layers were deposited on glass and flexible substrates. In each case, a systematic study was conducted in which all the relevant processing parameters were varied over a broad range. These studies indicated that the structural features of the substrate significantly influence the structural features of the semiconductor thin films. The flexible substrate (kapton) was characterized by the presence of ridges, which distorted the growth behavior of the films. Deposition of ln/Cu/ln metallic alloys onto Mo coated glass (kapton) resulted in discontinuous metallic alloys, which were characterized by the presence of separated elongated island structures. The structural features of the precursors were maintained in the absorber film after selenization in elemental Se vapor. The morphological features of the CulnSe₂ absorber films were also critically influenced by the reaction temperature And reaction period to Se. The structural features on a-Si:H was significantly influenced by the structural features of the particular substrate used. Atomic force microscopy (AFM) imaging in combination with statistical analysis revealed higher roughness values when the amorphous semiconductor materials were deposited onto kapton, which negatively impacts on the device properties of solar cell devices.

Amorphous Silicon(a-Si) films have attracted the attention of several investigators as it is an economical material for devices. One of the problems that is addressed is the doping of these films after they are prepared. In this thesis, we investigated the effects of doping amorphous Sil­icon films(prepared by r.f. sputtering) with Aluminium(Al) by ther­mal diffusion. Amorphous Silicon films have been prepared on glass substrates at optimal process parameters. Then, the a-Si films are coated with Al by vacuum evaporation and subjected to heating in N2 atmosphere in the temperature range 300°C to 600°C for different durations. After etching Al layer, it has been found that some of the films which are heated around 550°C contain filament like polycrystalline regions surrounding islands of a-Si. This structure has been confirmed through Scanning Electron Mi-croscope(SEM) photographs and electrical conductivity measurements. SEM photographs indicate that, bright regions of amorphous mate­rial are surrounded by dark regions of relatively higher conducting boundaries. The electrical conductivity study shows that there is sharp increase in conductivity of Al doped films, which is attributed to the conduct­ing polycrystalUne filament. A simple model has been proposed to explain the variation of con­ductivity of these transformed films, with process parameters and with temperature. Schottky barrier diodes have been fabricated using these trans­formed materials and their characteristics explained.

Indiana University-Purdue University Indianapolis (IUPUI) / In this research thesis, copper indium gallium selenium (CIGS) nanoparticles were synthesized from metal chlorides, functionalized to disperse in water, and further used in layer by layer (LbL) nanoassembly of CIGS films. CIGS nanoparticles were synthesized through the colloidal precipitation in an organic solvent. The peak and average sizes of the synthesized particles were measured to be 68 nm and 75 nm in chloroform, and 30 nm and 115 nm in water, respectively. Two methods were used to disperse the particle in water. In the first method the stabilizing agent oleylamine (OLA) was removed through multiple cleaning processes, and in the second method ligand exchange was performed with polystyrene sulfonate (PSS). Zeta potential of CIGS nanoparticles dispersed in water was measured to be +61 mV. The surface charge of the nanoparticles was reversed by raising the pH of the solution, which was measured to be −43.3 mV at 10.5 pH. In a separate process, the CIGS nanoparticles dispersed in water were coated with PSS. The resulting dispersion was observed to be stable and the surface charge was measured to be −56.9 mV. The LbL deposition process of CIGS nanoparticles was characterized by depositing thin films on quartz crystal microbalance (QCM). LbL depositions was conducted using (i) oppositely charged CIGS nanoparticles, (ii) positively charged CIGS nanoparticles and PSS, and (iii) PSS-coated CIGS (CIGS-PSS) and polyethyleneimine (PEI). The average thickness of each bi-layer of the above mentioned depositions were measured to be 2.2 nm, 1.37 nm, and 10.12 nm, respectively. The results from the QCM have been observed to be consistent with the film thickness results obtained from atomic force microscopy (AFM). Various immersion times versus thickness of the film were also studied. For electrical characterization, the CIGS films were deposited on indium tindioxide (ITO)-coated glass substrates. Current versus voltage (I/V) measurements were carried out for each of the films using the Keithley semiconductor characterization instruments and micromanipulator probing station. It was observed that the conductivity of the films was increased with the deposition of each additional layer. The I/V characteristics were also measured under the light illumination and after annealing to study the photovoltaic and annealing effects. It was observed that under light illumination, the resistivity of a 12-layer CIGS film decreased by 93% to 0.54 MΩ.m, and that of the same number of layers of PSS-coated CIGS and PEI film decreased by 60% to 0.97 MΩ.m under illumination. The resistivity of an 8-layer CIGS and PSS film decreased by 76.4% to 0.1 MΩ.m, and that of the same layers of PSS-coated CIGS and PEI decreased by 87% to 0.07 MΩ.m after annealing. The functionalized nanoparticles and the LbL CIGS films were implemented in the solar cell devices. Several configurations of CIGS films (p-type), and ZnO and CdS films (n-type) were considered. Poly(3,4-ethylenedioxythiophene) (PEDOT), molybdenum (Mo), and ITO were used as back contacts and ITO was used as front contact for all the devices. The devices were characterized the Keithley semiconductor characterization instruments and micromanipulator probing station. For a CIGS and n-ZnO films device with PEDOT as back contact and ITO as front contact, the current density at 0 V and under light illumination was measured to be 60 nA/cm2 and the power density was measured to be 0.018 nW/cm2. For a CIGS and CdS films device with ITO as both back and front contact, the current density at 0 V and under light illumination was measured to be 50 nA/cm2 and the power density was measured to be 0.01 nW/cm2. For a drop-casted CIGS and CdS films device with Mo as back contact and ITO as front contact, the current density of 50 nA/cm2 at 0 V and power density of 0.5 nW/cm2 under light illumination was measured. For the LbL CIGS and chemical bath deposited CdS films device with ITO as both back and front contact, the current density of 0.04 mA/cm2 at 0 V and power density of 1.6 μW/cm2 under light illumination was measured. Comparing to Device-III, an increase by 99% in the power density was observed by using the CIGS LbL film in the device structure. The novel aspects of this research include, (i) functionalization of the CIGS nanoparticles to disperse in water including coating with PSS, (ii) electrostatic LbL deposition of CIGS films using oppositely charged nanoparticles and polymers, and (iii) the utilization of the fabricated LbL CIGS films to develop solar cells. In addition, the n-type cadmium sulfide film (CdS) and zinc oxide (ZnO) buffer layer were also deposited through LbL process after the respective particles were functionalized with PSS coating in separate experiments.