Aqueous colloidal stability evaluated by zeta potential measurement and resultant TiO2 for superior photovoltaic performance

Controlling the morphological structure of titanium dioxide (TiO 2) is crucial for obtaining superior power conversion efficiency for dye-sensitized solar cells. Although the sol-gel-based process has been developed for this purpose, there has been limited success in resisting the aggregation of nanostructured TiO2, which could act as an obstacle for mass production. Herein, we report a simple approach to improve the efficiency of dye-sensitized solar cells (DSSC) by controlling the degree of aggregation and particle surface charge through zeta potential analysis. We found that different aqueous colloidal conditions, i.e., potential of hydrogen (pH), water/titanium alkoxide (titanium isopropoxide) ratio, and surface charge, obviously led to different particle sizes in the range of 10-500 nm. We have also shown that particles prepared under acidic conditions are more effective for DSSC application regarding the modification of surface charges to improve dye loading and electron injection rate properties. Power conversion efficiency of 6.54%, open-circuit voltage of 0.73 V, short-circuit current density of 15.32 mA/cm2, and fill factor of 0.73 were obtained using anatase TiO 2 optimized to 10-20 nm in size, as well as by the use of a compact TiO2 blocking layer.

Rational design of 3D dendritic TiO2 nanostructures with favorable architectures

Controlling the morphology and size of titanium dioxide (TiO2) nanostructures is crucial to obtain superior photocatalytic, photovoltaic, and electrochemical properties. However, the synthetic techniques for preparing such structures, especially those with complex configurations, still remain a challenge because of the rapid hydrolysis of Ti-containing polymer precursors in aqueous solution. Herein, we report a completely novel approach-three- dimensional (3D) TiO2 nanostructures with favorable dendritic architectures-through a simple hydrothermal synthesis. The size of the 3D TiO2 dendrites and the morphology of the constituent nano-units, in the form of nanorods, nanoribbons, and nanowires, are controlled by adjusting the precursor hydrolysis rate and the surfactant aggregation. These novel configurations of TiO2 nanostructures possess higher surface area and superior electrochemical properties compared to nanoparticles with smooth surfaces. Our findings provide an effective solution for the synthesis of complex TiO2 nano-architectures, which can pave the way to further improve the energy storage and energy conversion efficiency of TiO 2-based devices.

Influence of surfactant and annealing temperature on optical properties of sol-gel derived nano-crystalline TiO2 thin films

Titanium dioxide thin films have been synthesized by sol-gel spin coating technique on glass and silicon substrates with and without surfactant polyethylene glycol (PEG). XRD and SEM results confirm the presence of nano-crystalline (anatase) phase at an annealing temperature of 300 degrees C. The influence of surfactant and annealing temperature on optical properties of TiO2 thin films has been studied. Optical constants and film thickness were estimated by Swanepoel's (envelope) method and by ellipsometric measurements in the visible spectral range. The optical transmittance and reflectance were found to decrease with an increase in PEG percentage. Refractive index of the films decreased and film thickness increased with the increase in percentage of surfactant. The refractive index of the un-doped TiO2 films was estimated at different annealing temperatures and it has increased with the increasing annealing temperature. The optical band gap of pure TiO2 films was estimated by Tauc's method at different annealing temperature. (C) 2010 Elsevier B.V. All rights reserved.

Ultrastructure of Biofilms Formed by Bacteria from Industrial Processes

Microorganisms exist predominantly as sessile multispecies communities in natural habitats. Most bacterial species can form these matrix-enclosed microbial communities called biofilms. Biofilms occur in a wide range of environments, on every surface with sufficient moisture and nutrients, also on surfaces in industrial settings and engineered water systems. This unwanted biofilm formation on equipment surfaces is called biofouling. Biofouling can significantly decrease equipment performance and lifetime and cause contamination and impaired quality of the industrial product. In this thesis we studied bacterial adherence to abiotic surfaces by using coupons of stainless steel coated or not coated with fluoropolymer or diamond like carbon (DLC). As model organisms we used bacterial isolates from paper machines (Meiothermus silvanus, Pseudoxanthomonas taiwanensis and Deinococcus geothermalis) and also well characterised species isolated from medical implants (Staphylococcus epidermidis). We found that coating of steel surface with these materials reduced its tendency towards biofouling: Fluoropolymer and DLC coatings repelled all four biofilm formers on steel. We found great differences between bacterial species in their preference of surfaces to adhere as well as their ultrastructural details, like number and thickness of adhesion organelles they expressed. These details responded differently towards the different surfaces they adhered to. We further found that biofilms of D. geothermalis formed on titanium dioxide coated coupons of glass, steel and titanium, were effectively removed by photocatalytic action in response to irradiation at 360 nm. However, on non-coated glass or steel surfaces irradiation had no detectable effect on the amount of bacterial biomass. We showed that the adhesion organelles of bacteria on illuminated TiO2 coated coupons were complety destroyed whereas on non-coated coupons they looked intact when observed by microscope. Stainless steel is the most widely used material for industrial process equipments and surfaces. The results in this thesis showed that stainless steel is prone to biofouling by phylogenetically distant bacterial species and that coating of the steel may offer a tool for reduced biofouling of industrial equipment. Photocatalysis, on the other hand, is a potential technique for biofilm removal from surfaces in locations where high level of hygiene is required. Our study of natural biofilms on barley kernel surfaces showed that also there the microbes possessed adhesion organelles visible with electronmicroscope both before and after steeping. The microbial community of dry barley kernels turned into a dense biofilm covered with slimy extracellular polymeric substance (EPS) in the kernels after steeping in water. Steeping is the first step in malting. We also presented evidence showing that certain strains of Lactobacillus plantarum and Wickerhamomyces anomalus, when used as starter cultures in the steeping water, could enter the barley kernel and colonise the tissues of the barley kernel. By use of a starter culture it was possible to reduce the extensive production of EPS, which resulted in a faster filtration of the mash.

Studies on the brookite-rutile transformation

Brookite, the orthorhombic modification of titanium dioxide, transforms to the tetragonal modification, rutile, on heating. The kinetics and energetics of the transformation have been studied. Below 715±10°C, the rate of transformation is extremely slow. There appears to be little or no induction time. The kinetic data can be fitted reasonably well by the first-order equation. The energy of activation is about 60 kcal/mole and the frequency factor is of the order of 1013 h-1. The entropy of activation from Eyring's theory is about -18 cal/mole deg. at 800°C. The heat of this transformation is -100±75 cal/mole. The kinetic results may be explained qualitatively in terms of various analogies but more clearly by the application of the order-disorder theory to diffusionless transformation in solids. It has been shown that the ratio of propagation rate constant to the nucleation rate constant is small and that there is little or negligible phase aggregation.

Micropillar Array Based Microchips for Electrospray Ionization Mass Spectrometry, Microreactors, and Liquid Chromatographic Separation

This dissertation deals with the design, fabrication, and applications of microscale electrospray ionization chips for mass spectrometry. The microchip consists of microchannel, which leads to a sharp electrospray tip. Microchannel contain micropillars that facilitate a powerful capillary action in the channels. The capillary action delivers the liquid sample to the electrospray tip, which sprays the liquid sample to gas phase ions that can be analyzed with mass spectrometry. The microchip uses a high voltage, which can be utilized as a valve between the microchip and mass spectrometry. The microchips can be used in various applications, such as for analyses of drugs, proteins, peptides, or metabolites. The microchip works without pumps for liquid transfer, is usable for rapid analyses, and is sensitive. The characteristics of performance of the single microchips are studied and a rotating multitip version of the microchips are designed and fabricated. It is possible to use the microchip also as a microreactor and reaction products can be detected online with mass spectrometry. This property can be utilized for protein identification for example. Proteins can be digested enzymatically on-chip and reaction products, which are in this case peptides, can be detected with mass spectrometry. Because reactions occur faster in a microscale due to shorter diffusion lengths, the amount of protein can be very low, which is a benefit of the method. The microchip is well suited to surface activated reactions because of a high surface-to-volume ratio due to a dense micropillar array. For example, titanium dioxide nanolayer on the micropillar array combined with UV radiation produces photocatalytic reactions which can be used for mimicking drug metabolism biotransformation reactions. Rapid mimicking with the microchip eases the detection of possibly toxic compounds in preclinical research and therefore could speed up the research of new drugs. A micropillar array chip can also be utilized in the fabrication of liquid chromatographic columns. Precisely ordered micropillar arrays offer a very homogenous column, where separation of compounds has been demonstrated by using both laser induced fluorescence and mass spectrometry. Because of small dimensions on the microchip, the integrated microchip based liquid chromatography electrospray microchip is especially well suited to low sample concentrations. Overall, this work demonstrates that the designed and fabricated silicon/glass three dimensionally sharp electrospray tip is unique and facilitates stable ion spray for mass spectrometry.

Properties of ion assisted deposited titania films

Thin films of titanium dioxide have been deposited using ion assisted deposition with oxygen ions in the energy range 100�500 eV and current densities up to 100 ?A/cm2. It has been observed that the refractive index of the films increases up to 300 eV and the extinction coefficient increased only nominally up to 300 eV. Optical band gap calculations have shown a strong dependence of the gap on the energy of incident ions. Beyond a critical energy and current density of the ions the refractive index and extinction coefficient of the films start deteriorating. It has also been found that beyond the critical values the optical band gap value decreases. The maximum refractive index obtained was 2.49 at an energy of 300 eV and 50 ?A/cm2 current density. Post?deposition annealing of the films at 500?°C resulted in a slight increase in refractive index without affecting the extinction coefficient. X?ray diffraction studies revealed a monophasic anatase structure in these films. ?

Structural characterization of DC magnetron-sputtered TiO2 thin films using XRD and Raman scattering studies

Titanium dioxide films have been deposited using DC magnetron sputtering technique onto well-cleaned p-silicon substrates at an oxygen partial pressure of 7 x 10(-5) mbar and at a sputtering pressure (Ar + O-2) Of I X 10(-3) mbar. The deposited films were calcinated at 673 and 773 K. The composition of the films as analyzed using Auger electron spectroscopy reveals the stoichiometry with an 0 and Ti ratio 2.08. The influence of post-deposition annealing at 673 and 773 K on the structural properties of the titanium dioxide thin films have been studied using XRD and Raman scattering. The structure of the films deposited at the ambient was found to be amorphous and the films annealed at temperature 673 K and above were crystalline with anatase structure. The lattice constants, grain size, microstrain and the dislocation density of the film are calculated and correlated with annealing temperature. The Raman scattering study was performed on the as-deposited and annealed samples and the existence of Raman active modes A(1g), B-1g and E-g corresponding to the Raman shifts are studied and reported. The improvement of crystallinity of the TiO2 films was also studied using Raman scattering studies. (C) 2003 Elsevier Ltd. All rights reserved.

Optical, electrical and dielectric properties of TiO(2)-SiO(2) films prepared by a cost effective sol-gel process

Titanium dioxide (TiO(2)) and silicon dioxide (SiO(2)) thin films and their mixed films were synthesized by the sol-gel spin coating method using titanium tetra isopropoxide (TTIP) and tetra ethyl ortho silicate (TEOS) as the precursor materials for TiO(2) and SiO(2) respectively. The pure and composite films of TiO(2) and SiO(2) were deposited on glass and silicon substrates. The optical properties were studied for different compositions of TiO(2) and SiO(2) sols and the refractive index and optical band gap energies were estimated. MOS capacitors were fabricated using TiO(2) films on p-silicon (1 0 0) substrates. The current-voltage (I-V) and capacitance-voltage (C-V) characteristics were studied and the electrical resistivity and dielectric constant were estimated for the films annealed at 200 degrees C for their possible use in optoelectronic applications. (C) 2011 Elsevier B.V. All rights reserved.

Effect of substrate bias voltage on the structure, electric and dielectric properties of TiO(2) thin films by DC magnetron sputtering

Titanium dioxide (TiO(2)) films have been deposited on glass and p-silicon (1 0 0) substrates by DC magnetron sputtering technique to investigate their structural, electrical and optical properties. The surface composition of the TiO(2) films has been analyzed by X-ray photoelectron spectroscopy. The TiO(2) films formed on unbiased substrates were amorphous. Application of negative bias voltage to the substrate transformed the amorphous TiO(2) into polycrystalline as confirmed by Raman spectroscopic studies. Thin film capacitors with configuration of Al/TiO(2)/p-Si have been fabricated. The leakage current density of unbiased films was 1 x10(-6) A/cm(2) at a gate bias voltage of 1.5 V and it was decreased to 1.41 x 10(-7) A/cm(2) with the increase of substrate bias voltage to -150 V owing to the increase in thickness of interfacial layer of SiO(2). Dielectric properties and AC electrical conductivity of the films were studied at various frequencies for unbiased and biased at -150 V. The capacitance at 1 MHz for unbiased films was 2.42 x 10(-10) F and it increased to 5.8 x 10(-10) F in the films formed at substrate bias voltage of -150 V. Dielectric constant of TiO(2) films were calculated from capacitance-voltage measurements at 1 MHz frequency. The dielectric constant of unbiased films was 6.2 while those formed at -150 V it increased to 19. The optical band gap of the films decreased from 3.50 to 3.42 eV with the increase of substrate bias voltage from 0 to -150 V. (C) 2011 Elsevier B. V. All rights reserved.

Substrate temperature influenced physical properties of silicon MOS devices with TiO2 gate dielectric

DC reactive magnetron sputtering technique was employed for deposition of titanium dioxide (TiO2) films. The films were formed on Corning glass and p-Si (100) substrates by sputtering of titanium target in an oxygen partial pressure of 6x10-2 Pa and at different substrate temperatures in the range 303 673 K. The films formed at 303 K were X-ray amorphous whereas those deposited at substrate temperatures?=?473 K were transformed into polycrystalline nature with anatase phase of TiO2. Fourier transform infrared spectroscopic studies confirmed the presence of characteristic bonding configuration of TiO2. The surface morphology of the films was significantly influenced by the substrate temperature. MOS capacitor with Al/TiO2/p-Si sandwich structure was fabricated and performed currentvoltage and capacitancevoltage characteristics. At an applied gate voltage of 1.5 V, the leakage current density of the device decreased from 1.8?x?10-6 to 5.4?x?10-8 A/cm2 with the increase of substrate temperature from 303 to 673 K. The electrical conduction in the MOS structure was more predominant with Schottky emission and Fowler-Nordheim conduction. The dielectric constant (at 1 MHz) of the films increased from 6 to 20 with increase of substrate temperature. The optical band gap of the films increased from 3.50 to 3.56 eV and refractive index from 2.20 to 2.37 with the increase of substrate temperature from 303 to 673 K. Copyright (c) 2012 John Wiley & Sons, Ltd.

Shape Effect on Electronic and Photovoltaic Properties of CdS Nanocrystals

Changes in electronic and photovoltaic properties of semiconductor nanocrystals predominantly due to changes in shape are discussed here. Cadmium sulfide (CdS) semiconductor nanocrystals of various shapes (tetrapod, tetrahedron, sphere and rod) obtained using an optimized solvothermal process exhibited a mixed cubic (zinc blende) and hexagonal (wurtzite) crystal structure. The simultaneous presence of the two crystal phases in varying amounts is observed to play a pivotal role in determining both the electronic and photovoltaic properties of the CdS nanocrystals. Light to electrical energy conversion efficiencies (measured in two-electrode configuration laboratory solar cells) remarkably decreased by one order in magnitude from tetrapod -> tetrahedron -> sphere -> rod. The tetrapod-CdS nanocrystals, which displayed the highest light to electrical energy conversion efficiency, showed a favorable shift in position of the conduction band edge leading to highest rate of electron injection (from CdS nanocrystal to the wide band gap semiconductor viz, titanium dioxide, TiO2) and lowest rate of electron-hole recombination (higher free electron lifetimes).

Influence of annealing temperature on Raman and photoluminescence spectra of electron beam evaporated TiO2 thin films

Titanium dioxide (TiO2) thin films were deposited on fused quartz substrates by electron beam evaporation method at room temperature. The films were annealed at different temperatures in ambient air. The surface morphology/roughness at different annealing temperatures were analyzed by atomic force microscopy (AFM). The crystallinity of the film has improved with the increase of annealing temperature. The effect of annealing temperature on optical, photoluminescence and Raman spectra of TiO2 films were investigated. The refractive index of TiO2 films were studied by envelope method and reflectance spectra and it is observed that the refractive index of the films was high. The photoluminescence intensity corresponding to green emission was enhanced with increase of annealing temperature. The peaks in Raman spectra depicts that the TiO2 film is of anatase phase after annealing at 300 degrees C and higher. The films show high refractive index, good optical quality and photoluminescence characteristics suggest that possible usage in opto-electronic and optical coating applications. (C) 2012 Elsevier B.V. All rights reserved.

Photocatalytic degradation with combustion synthesized WO3 and WO3-TiO2 mixed oxides under UV and visible light

The photocatalytic activity of commercial titanium dioxide under UV and visible radiation was improved by composites of tungsten trioxide (WO3) with TiO2. WO3 was prepared by solution combustion synthesis and the mixed oxides/composites of WO3-TiO2 were prepared in different weight ratios (0, 0.10, 0.15, 0.20, 0.25, 0.50, 0.75, and 1) by physical mixing. These catalysts were characterized by XRD, DRS, BET, SEM, TEM, pH drift method, TGA and photoluminescence. The photocatalytic activity varies with the WO3 loading in the composites. The optimum loading of WO3 in the composites was found to be 15 wt% for both UV and visible radiation. This loading showed faster dye degradation rate than commercial TiO2 (TiO2-C) and WO3 (WO3-C). The effect of initial concentrations of methylene blue (MB) and orange G (OG) and the effect of the functional group on dye degradation was studied with both anionic and cationic dyes with 15 wt% WO3-TiO2. (C) 2012 Elsevier B.V. All rights reserved.

Structural, electrical and dielectric properties of sputtered TiO2 films for Al/TiO2/Si capacitors

Metal-oxide semiconductor capacitors based on titanium dioxide (TiO2) gate dielectrics were prepared by RF magnetron sputtering technique. The deposited films were post-annealed at temperatures in the range 773-1173 K in air for 1 hour. The effect of annealing temperature on the structural properties of TiO2 films was investigated by X-ray diffraction and Raman spectroscopy, the surface morphology was studied by atomic force microscopy (AFM) and the electrical properties of Al/TiO2/p-Si structure were measured recording capacitance-voltage and current-voltage characteristics. The as-deposited films and the films annealed at temperatures lower than 773 K formed in the anatase phase, while those annealed at temperatures higher than 973 K were made of mixtures of the rutile and anatase phases. FTIR analysis revealed that, in the case of films annealed at 1173 K, an interfacial layer had formed, thereby reducing the dielectric constant. The dielectric constant of the as-deposited films was 14 and increased from 25 to 50 with increases in the annealing temperature from 773 to 973 K. The leakage current density of as-deposited films was 1.7 x 10(-5) and decreased from 4.7 X 10(-6) to 3.5 x 10(-9) A/cm(2) with increases in the annealing temperature from 773 to 1173 K. The electrical conduction in the Al/TiO2/p-Si structures was studied on the basis of the plots of Schottky emission, Poole-Frenkel emission and Fowler-Nordheim tunnelling. The effect of structural changes on the current-voltage and capacitance-voltage characteristics of Al/TiO2/p-Si capacitors was also discussed.