Investigations on TiO2 Based Nanocomposites as Potential Photonic Materials

This Study overviews the basics of TiO2with respect to its structure, properties and applications. A brief account of its structural, electronic and optical properties is provided. Various emerging technological applications utilising TiO2 is also discussed.Till now, exceptionally large number of fundamental studies and application-oriented research and developments has been carried out by many researchers worldwide in TiO2 with its low-dimensional nanomaterial form due to its various novel properties. These nanostructured materials have shown many favourable properties for potential applications, including pollutant photocatalytic decomposition, photovoltaic cells, sensors and so on. This thesis aims to make an in-depth investigation on different linear and nonlinear optical and structural characteristics of different phases of TiO2. Correspondingly, extensive challenges to synthesise different high quality TiO2 nanostructure derivatives such as nanotubes, nanospheres, nanoflowers etc. are continuing. Here, different nanostructures of anatase TiO2 were synthesised and analysed. Morphologically different nanostructures were found to have different impact on their physical and electronic properties such as varied surface area, dissimilar quantum confinement and hence diverged suitability for different applications. In view of the advantages of TiO2, it can act as an excellent matrix for nanoparticle composite films. These composite films may lead to several advantageous functional optical characteristics. Detailed investigations of these kinds of nanocomposites were also performed, only to find that these nanocomposites showed higher adeptness than their parent material. Fine tuning of these parameters helps researchers to achieve high proficiency in their respective applications. These innumerable opportunities aims to encompass the new progress in studies related to TiO2 for an efficient utilization in photo-catalytic or photo-voltaic applications under visible light, accentuate the future trends of TiO2-research in the environment as well as energy related fields serving promising applications benefitting the mankind. The last section of the thesis discusses the applicability of analysed nanomaterials for dye sensitised solar cells followed by future suggestions.

Thermo- Optic and Nonlinear-Optical studies on CdSe Quantum Dots for Photonic Applications

In general, linear- optic, thermo- optic and nonlinear- optical studies on CdSe QDs based nano uids and their special applications in solar cells and random lasers have been studied in this thesis. Photo acous- tic and thermal lens studies are the two characterization methods used for thermo- optic studies whereas Z- scan method is used for nonlinear- optical charecterization. In all these cases we have selected CdSe QDs based nano uid as potential photonic material and studied the e ect of metal NPs on its properties. Linear optical studies on these materials have been done using vari- ous characterization methods and photo induced studies is one of them. Thermal lens studies on these materials give information about heat transport properties of these materials and their suitability for applica- tions such as coolant and insulators. Photo acoustic studies shows the e ect of light on the absorption energy levels of the materials. We have also observed that these materials can be used as optical limiters in the eld of nonlinear optics. Special applications of these materials have been studied in the eld of solar cell such as QDSSCs, where CdSe QDs act as the sensitizing materials for light harvesting. Random lasers have many applications in the eld of laser technology, in which CdSe QDs act as scattering media for the gain.

Investigation of cadmium alternatives in thin-film coatings - art. no. 62860C

The health risks associated with the inhalation or ingestion of cadmium are well documented([1,2]). During the past 18 years, EU legislation has steadily been introduced to restrict its use, leaving a requirement for the development of replacement materials. This paper looks at possible alternatives to various cadmium II-VI dielectric compounds used in the deposition of optical thin-films for various opto-electronic devices. Application areas of particular interest are for infrared multilayer interference filter fabrication and solar cell industries, where cadmium-based coatings currently find widespread use. The results of single and multilayer designs comprising CdTe, CdS, CdSe and PbTe deposited onto group IV and II-VI materials as interference filters for the mid-IR region are presented. Thin films of SnN, SnO2, SnS and SnSe are fabricated by plasma assisted CVD, reactive RF sputtering and thermal evaporation. Examination of these films using FTIR spectroscopy, SEM, EDX analysis and optical characterisation methods provide details of material dispersion, absorption, composition, refractive index, energy band gap and layer thicknesses. The optimisation of deposition parameters in order to synthesise coatings with similar optical and semiconductor properties as those containing cadmium has been investigated. Results of environmental, durability and stability trials are also presented.

ATP pulse and calcium homeostasis in cells from hepatopancreas of Dilocarcinus pagei, a freshwater crab

Calcium (Ca) is critical for crustaceans due to their molting cycle and its presence in the carapace as calcium carbonate, apart from the usual functions of Ca, such as cell signalling. Ca transport in Dilocarcinus pagei, a freshwater crab, was studied in isolated cells from hepatopancreas to further characterize Ca transport mechanisms in these crabs. Cells were isolated and loaded with Fluo-3, a calcium fluorescent dye. Three different cell treatments were performed: Group 1 cells were Ca free during cell dissociation, and calcium was present (at 1mM) for fluorescence cell loading and transport experiments (FC); Group 2 cells were calcium free during cell dissociation and for transport experiments, but not during cell loading (LC); and Group 3 cells were Ca free during cell dissociation, cell loading and transport experiments (WC). Intracellular Ca was recorded through time after ATP was added to the cells and ATP caused an increase in Ca efflux within 30s in all cells. WC cells showed the smallest Ca efflux compared to the other cells, probably because it was intracellularly Ca ""depleted"". Vanadate and amiloride decreased the Ca efflux when ATP was added to the cells, while verapamil did not cause any effect in Ca efflux, confirming the presence of a Ca(2+)-ATPase sensitive to vanadate in hepatopancreas of D. pagei. In a different set of experiments, cells were also exposed to a Ca pulse of 1 and 10mM during 180s. 10mM Ca increased intracellular Ca compared to 1mM, and the increase was not recovered during the experimental time. Additionally, Ca influx was reduced by verapamil and amiloride, but not completely. The results suggest that Ca influx probably occurs through an undefined exchanger, apart from Ca channels (verapamil sensitive) and electrogenic 1Na(+)(1H(+))/1 Ca(2+) exchanger (amiloride-sensitive). Similarities between freshwater and seawater crabs, lobsters and crayfish in relation to plasma membrane Ca transporters, although the environment where they live is quite diverse, suggest that universal mechanisms for Ca homeostasis are widespread among crustaceans. (C) 2010 Elsevier Inc. All rights reserved.

Substitutional Impurities in PPV Crystals: An Intrinsic Donor-Acceptor System for High V(oc) Photovoltaic Devices

Defects are usually present in organic polymer films and are commonly invoked to explain the low efficiency obtained in organic-based optoelectronic devices. We propose that controlled insertion of substitutional impurities may, on the contrary, tune the optoelectronic properties of the underivatized organic material and, in the case studied here, maximize the efficiency of a solar cell. We investigate a specific oxygen-impurity substitution, the keto-defect -(CH(2)-C=O)- in underivatized crystalline poly(p-phenylenevinylene) (PPV), and its impact on the electronic structure of the bulk film, through a combined classical (force-field) and quantum mechanical (DFT) approach. We find defect states which suggest a spontaneous electron hole separation typical of a donor acceptor interface, optimal for photovoltaic devices. Furthermore, the inclusion of oxygen impurities does not introduce defect states in the gap and thus, contrary to standard donor-acceptor systems, should preserve the intrinsic high open circuit voltage (V(oc)) that may be extracted from PPV-based devices.

Electrocatalytic oxidation of urea by nanostructured nickel/cobalt hydroxide electrodes

The present paper describes the catalytic oxidation of urea performed by nickel hydroxide and nickel/cobalt hydroxide modified electrodes by using both electrodeposited films and nanoparticles. The incorporation of Co foreign atoms leads to a slight increase in sensitivity besides the shift in redox process, avoiding the oxygen reaction. Nanostructured Ni80Co20(OH)(2) was synthesized by sonochemical route producing 5 nm diameter particles characterized by high-resolution transmission electron microscopy (HRTEM) being immobilized onto electrode by using the electrostatic Layer-by-layer technique, yielding attractive modified electrodes for sensor development. (C) 2007 Elsevier Ltd. All rights reserved.

Interfacial Electron Transfer Dynamics Following Laser Flash Photolysis of [Ru(bpy)(2)((4,4 `-PO(3)H(2))(2)bpy)](2+) in TiO(2) Nanoparticle Films in Aqueous Environments

Nanosecond laser flash photolysis has been used to investigate injection and back electron transfer from the complex [(Ru-(bpy)(2)(4,4`-(PO(3)H(2))(2)bpy)](2+) surface-bound to TiO(2) (TiO(2)-Ru(II)). The measurements were conducted under conditions appropriate for water oxidation catalysis by known single-site water oxidation catalysts. Systematic variations in average lifetimes for back electron transfer, - were observed with changes in pH, surface coverage, incident excitation intensity, and applied bias. The results were qualitatively consistent with a model involving rate-limiting thermal activation of injected electrons from trap sites to the conduction band or shallow trap sites followed by site-to-site hopping and interfacial electron transfer, TiO(2)(e(-))-Ru(3+) -> TiO(2)-Ru(2+). The appearance of pH-dependent decreases in the efficiency of formation of TiO(2)-Ru(3+) and in incident-photon-to-current efficiencies with the added reductive scavenger hydroquinone point to pH-dependent back electron transfer processes on both the sub-nanosecond and millisecond-microsecond time scales, which could be significant in limiting long-term storage of multiple redox equivalents.

Active cooling of low-concentrating hybrid PV/Thermal collectors

A series of measurements on the performance of solar cell string modules with low-concentrating CPC reflectors with a concentration factor C ˜ 4X have been carried out. To minimise the reduction in efficiency due to high cell temperatures, the modules were cooled. Four different way of cooling were tested:1) The thermal mass of the module was increased, 2) passive air cooling was used by introducing a small air gap between the module and the reflector, 3) the PV cells were cooled by a large cooling fin, 4) the module was actively cooled by circulating cold water on the back. The best performance was given with the actively cooled PV module which gave 2,2 times the output from a reference module while for the output from the module with a cooling fin the value was 1,8.Active cooling is also interesting due to the possibility of co-generation of thermal and electrical energy which is discussed in the paper. Simulations, based on climate data from Stockholm, latitude 59.4°N, show that there are good prospects for producing useful temperatures of the cooling fluid with only a slightly reduced performance of the electrical fraction of the PV thermal hybrid system.

Thermal Evaluation of a Solarus PV-T collector

Low concentrator PV-T hybrid systems produce both electricity and thermal energy; this fact increases the overall efficiency of the system and reduces the cost of solar electricity. These systems use concentrators which are optical devices that concentrate sunlight on to solar cells and reduce expensive solar cell area. This thesis work deals with the thermal evaluation of a PV-T collector from Solarus.Firstly the thermal efficiency of the low concentrator collector was characterized for the thermal-collector without PV cells on the absorber. Only two types of paint were on the absorber, one for each trough of the collector. Both paints are black one is glossy and the other is dull,. The thermal efficiency at no temperature difference between collector and ambient for these two types of paint was 0.65 and 0.64 respectively; the U-value was 8.4 W/m2°C for the trough with the glossy type of paint and 8.6 W/m2°C for the trough with dull type of paint. The annual thermal output of these two paints was calculated for two different geographic locations, Casablanca, Morocco and Älvkarleby, Sweden.Secondly the thermal efficiency was defined for the PV-T collector with PV cells on the absorber. The PV cells cover 85% of the absorber, without any paint on the rest of the absorber area. We also tested how the electrical power output influences the thermal power output of the PV-T collector. The thermal and total performances for the PV-T collector were only characterized with reflector sides, because of the lack of time we could not characterize them with transparent sides also.

New approach to controllable nitrogen doping for improved nano-semiconductors

The data covers the following:
X-ray photoelectron spectroscopy (XPS) - to collect surface chemical structure changes (using RMIT instrument);
Scanning electron microscopy (SEM) - to collect surface physical structure changes;
Atomic force microscopy (AFM) - to collect surface morphology changes;
Internal/External quantum efficiency (IQE/EQE) – to collect DSSC (Dye Sensitised Solar Cells) efficiency data;
Discharge/Charge capacity - to collect battery efficiency data.

Recent progress in the development and use of organic ionic plastic crystal electrolytes

Significant progress has been made recently in the development of Organic Ionic Plastic Crystals (OIPCs), a unique family of solid state electrolytes with applications in electrochemical devices such as lithium batteries and dye-sensitised solar cells. The negligible volatility of OIPCs renders them more suitable than molecular species for long-term device use, while the high thermal and electrochemical stability of many OIPCs fulfils an essential requirement for solid state electrolytes for many device applications. However, the complex mechanisms of conduction through these materials, both in their pure state and in the presence of a small amount of a second component (such as lithium salts to enable their use in lithium batteries) are still not fully understood. At the same time, the range of anions and cations utilised in the synthesis of plastic crystal phases continues to increase. This perspective concentrates on recent research into both fundamental and device-oriented aspects of these materials. Important fundamental understanding of the physical properties and transport mechanisms of different OIPCs has been achieved through use of techniques including variable temperature solid-state NMR and crystallographic analysis, as well as detailed molecular dynamics simulations. In parallel, the applicability of these materials as electrolytes for dye-sensitised solar cells and lithium batteries is being more widely demonstrated. The possibility of using OIPCs as solid state electrolytes for fuel cells is also discussed.

An organic ionic plastic crystal electrolyte for rate capability and stability of ambient temperature lithium batteries

Reliable, safe and high performance solid electrolytes are a critical step in the advancement of high energy density secondary batteries. In the present work we demonstrate a novel solid electrolyte based on the organic ionic plastic crystal (OIPC) triisobutyl(methyl)phosphonium bis(fluorosulfonyl)imide (P1444FSI). With the addition of 4 mol% LiFSI, the OIPC shows a high conductivity of 0.26 mS cm-1 at 22 °C. The ion transport mechanisms have been rationalized by compiling thermal phase behaviour and crystal structure information obtained by variable temperature synchrotron X-ray diffraction. With a large electrochemical window (ca. 6 V) and importantly, the formation of a stable and highly conductive solid electrolyte interphase (SEI), we were able to cycle lithium cells (LiLiFePO4) at 30 °C and 20 °C at rates of up to 1 C with good capacity retention. At the 0.1 C rate, about 160 mA h g-1 discharge capacity was achieved at 20 °C, which is the highest for OIPC based cells to date. It is anticipated that these small phosphonium cation and [FSI] anion based OIPCs will show increasing significance in the field of solid electrolytes.

Ionic liquids for energy, materials, and medicine.

As highlighted by the recent ChemComm web themed issue on ionic liquids, this field continues to develop beyond the concept of interesting new solvents for application in the greening of the chemical industry. Here some current research trends in the field will be discussed which show that ionic liquids research is still aimed squarely at solving major societal issues by taking advantage of new fundamental understanding of the nature of these salts in their low temperature liquid state. This article discusses current research trends in applications of ionic liquids to energy, materials, and medicines to provide some insight into the directions, motivations, challenges, and successes being achieved with ionic liquids today.

Recent developments in electrospinning of nanofiber yarns

Nanofibers possess high surface area and excellent porosity. Though nanofibers can be produced by a variety of techniques, electrospinning stands distinct because of its simplicity and flexibility in processing different polymer materials, and ability to control fiber diameter, morphology, orientation, and chemical component. Nonetheless, electrospun nanofibers are predominantly produced in the form of randomly oriented fiber webs, which restrict their wide use. Converting nanofibers into twisted continuous bundles, i.e., nanofiber yarns, can improve their strength and facilitate their subsequent processes, but remains challenging to make. Nanofiber yarns also create enormous opportunities to develop well-defined three-dimensional nanofibrous architectures. This review article gives an overview of the state-of-the-art techniques for electrospinning of nanofiber yarns and control of nanofiber alignment. A detailed account on techniques to produce twisted/non-twisted short bundles and continuous yarns are discussed.

Taxa de absorção atmosférica sobre as cidades de Botucatu-SP e Rio de Janeiro-RJ

O segundo satélite da Missão Espacial Completa Brasileira (SCD2/MECB) foi colocado em órbita em 23 de Outubro de 1998 e carrega a bordo um experimento de células solares. Célula solar de silício é um dispositivo semicondutor, que pode medir a intensidade da radiação visível e parte da radiação infravermelha (400-1100 nm). O experimento permite medir simultaneamente a insolação direta e parte da radiação solar que é refletida pela Terra para o espaço. Os dados do experimento célula solar são transmitidos em tempo real pela telemetria do satélite e recebidos pela estação terrestre em Cuiabá, MT-Brasil (16°S; 56°W). Este fato limita a cobertura espacial para um círculo sobre a América do Sul. O albedo planetário é obtido dentro desta cobertura e seus valores podem ser agrupados em períodos temporais (anual, sazonal ou mensal), ou podem ser estudados para várias localizações (latitude e longitude) durante a vida do satélite. O coeficiente de transmissão atmosférica ou índice de claridade (Kt), medido em estações meteorológicas na superfície da Terra, junto com o valor medido simultaneamente do albedo planetário, permite calcular o coeficiente de absorção atmosférica (Ka). O método desenvolvido neste trabalho para avaliar Ka considera que o albedo planetário é composto por duas partes: uma refletividade local e uma refletividade não local. Considerando este novo conceito, é definida uma taxa de absorção atmosférica (denominada Ra) que é a razão entre Ka e a potência de irradiância solar líquida, que não atravessou a atmosfera (100%-Kt). A taxa de absorção atmosférica assim definida é independente da cobertura de nuvens. O histograma de freqüência de Ra mostra os valores de 0,86±0,07 e 0,88±0,09 sobre as cidades de Botucatu-SP e do Rio de Janeiro-RJ, durante os anos de 1999 até 2006, respectivamente.