With the combination of ferroelectric, ferromagnetic and the mutual coupling properties, multiferroics attracts a lot of researcher's attentions recently. Among of which BiFeO3 has caught extensive attention for it manifests multiferroic effects above the room temperature. However, the instability of Bi serious electric leakage is the major drawback. From early study in our group, it was found the Pb doping at Bi sites could stabilize Bi1-xPbxFeO3 phase . In this research Bi1-xPbxFeO3 compound is, then, used to grow films. The goal of this thesis is to understand how the grown conditions and their mechanism in affecting the properties of films. Bi0.9Pb0.1FeO3 target was formed by a solid state reaction method,Bi0.9Pb0.1FeO3 films were deposited by RF sputtering system on top of the SrRuO3 thin film which was pre-grown on the SrTiO3 (001) substrate as a conducting layer. It is found that the relative position between target and substrate is important for film growth. By analizing the AFM, XRD and EDS data, the grain sizes, the length of c-axis and the content of films are dependent on the growth temperature.

Thesis (Ph. D.)--University of Hong Kong, 2001. / Includes bibliographical references.

Thesis (M.S.) in Electrical Engineering--University of Maine, 2009. / Includes vita. Includes bibliographical references (leaves 110-113).

published_or_final_version / abstract / toc / Electrical and Electronic Engineering / Doctoral / Doctor of Philosophy

published_or_final_version / Electrical and Electronic Engineering / Master / Master of Philosophy

This thesis developed thin film extraction technique, which is a solid phase microextraction (SPME) technique with enhanced sensitivity, without sacrificing analysis time due to the large surface area-to-volume ratio of thin film. Thin film extraction was applied for both spot sampling and time weighted average (TWA) sampling in laboratory and on site. First, an electric drill coupled with a SPME polydimethylsiloxane (PDMS) fiber or a PDMS thin film was used for active spot sampling of polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. Laboratory experiments demonstrated that the sampling rates of fiber and thin film can be predicted theoretically. The performance of a PDMS-coated stir bar at a constant stirring speed was also investigated. Compared with the fiber or the stir bar, the thin film sampler exhibited a higher sampling rate and much better sensitivity due to its higher surface-to-volume ratio and its larger extraction-phase volume. A new thin film active sampler was developed; field tests illustrated that it was excellent for rapid on-site water sampling due to its short sampling period, high sampling efficiency and durability. Second, modeling was applied to study the kinetics of fiber SPME and thin film extraction by COMSOL Multiphysics. The symmetry of absorption of analyte onto the fiber (or thin film) and desorption of calibrant from the fiber in static aqueous solution and a flow through system, was demonstrated by modeling. Furthermore, kinetic calibration method was illustrated to be feasible for fiber SPME in complex aqueous matrix and then was used to calculate the total concentration of analyte in the system. Third, thin film extraction was used in on-site sampling in Hamilton Harbour and for the determination of TWA concentrations of PAHs based on the kinetic calibration. When the thin film sampler, a fiber-retracted SPME field water sampler, and a SPME rod were used simultaneously, the thin film sampler exhibited the highest sampling rate compared to the other water samplers, due to its large surface-to-volume ratio. Fourth, partition equilibriums and extraction rates of PAHs were examined for live biomonitoring with black worms and for the PDMS thin-film in passive sampling mode. In the initial extraction stage, the extracted amounts per surface area by two samplers were similar indicating that thin-film samplers could mimic the behavior of black worms for passive monitoring. A good linear relationship between bioconcentration factors and film-water partition coefficients of PAHs demonstrated the feasibility of thin-film sampler for determining the bioavailability of PAHs in water. Finally, thin film extraction was used for the analysis of human skin and breath under different experimental conditions. Thin film technique could study several skin areas of one person, characterize the skins of different persons, and measure volatile fractions of cosmetic products that were released from the skin. The sampling time in the breath analysis could be further reduced to only 20 seconds when the thin film was rotated with a portable drill.

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Interest in the Langmuir-Blodgett (LB) technique has led to a number of investigations into different types of materials that can be deposited in the form of monolayers. For example, as well as the classic long Cham fatty acids and alcohols, materials such as polymerisable molecules, aromatic hydrocarbons and dye substances can now all be produced in monomolecular form. Unfortunately, few of these materials yet fulfil the requirements of mechanical and thermal stability that will be necessary if LB films are to be used commercially. This work has dealt with the use of phthalocyanine, a substance well known for its thermal and chemical stability, in the production of LB films. Initially two compounds were investigated, dilithlum phthalocyanine and tetra-tert-butyl phthalocyanine. Although it was found that both materials produced layers of reproducible quality which adhered tenaciously to various substrates and to each other, single monolayers were not obtained. More success has been achieved using an asymmetrically substituted phthalocyanine molecule. Electron microscopy studies have shown that the majority of films are polycrystalline. However, a substitute CuPc proved to be a valuable exception. Multilayer films of this molecule were found to have domains of the order of 3 mm in size showing a preferred orientation. Even so, it has to be accepted that the phthalocyanine films produced to date are not as structurally perfect as for example, multilayers of lo-tricosenoic acid. Our ability to produce monomolecular layers of phthalocyanine now extends the range of possible applications for this material. For instance it is known that the fine control of insulator thickness is crucial in the optimisation of photovoltaic and electroluminescent metal-lnsulator-semlconductor devices. Examples of both types of device have been demonstrated using our phthalocyaine films. For the bistable switch, a gallium arsenide substrate was used; both gallium phosphide and zinc selenlde have been utilized in the electroluminescent structures. Moreover, In the case of phthalocyanine another possibility presents Itself. It has long been known that the conductivities of this material and its derivatives are very sensitive to the presence of certain gases, particularly the oxides of nitrogen. The increased conductivity of such materials has been demonstrated to be confined to the surface of the crystal. Hence many phthalocyanine gas detector systems have been based on thin films. Unfortunately because phthalocyanine exhibits polymorphism, the exact structure of such films can be complicated. making interpretation of results and subsequent device optimisation difficult. Also the response and recovery times of these thin film devices can also be excessively long. It is possible that monomolecular LB films of phthalocyanine could well overcome some or all of these problems. Our experiments have concentrated on asymmetrically substituted copper phthalocyanine and its usefulness to detect nitrogen dioxide. Preliminary results show the response and recovery times for the simple gas structures to be faster than those previously reported for other thin film phthalocyanine devices. It is suggested that this is due to the more ordered structure of the LB film, which enables the gas to adsorb on, or desorb from the molecular sites more readily.