Three non-peripherally substituted liquid crystalline bisphthalocyanine (Pc) compounds have been studied to examine the role of central metal ions lutetium (Lu), and gadolinium (Gd) and substituent chain lengths, i.e. octyl (C8H17) and hexyl (C6H13), in determining the physical properties. For the octyl substituted Pc molecules, the head-to-tail or Jaggregates within the as-deposited spun films produced a redshift of the optical absorption Q bands in relation to their 0.01 mgml-1 solutions. Annealing at 80˚C produced a well-ordered discotic liquid crystalline (LC) mesophase causing additional redshifts irrespective of the metal ion in case of C8LuPc2 and C8GdPc2. Formation of face-to-face or H-aggregated monomers led to blueshifts of the Q bands with respect to solution spectra for C6GdPc2, both as-deposited and annealed films. Stretching and bending vibrations of pyrrole, isoindole, and metal-nitrogen bonds in Pc rings showed Raman bands at higher energy for smaller metal ion. However, no change was observed for the difference in chain lengths. As-deposited C8LuPc2 and C6GdPc2 produced comparable Ohmic conductivity, of the value 67.55 Scm-1 and 42.31 Scm-1, respectively. C8GdPc2 exhibited two orders of magnitude less conductivity than the other two due to the size effect of the central ion and side chain length. On annealing, an increase of Ohmic conductivity was noticed in the isostructural octyl substituted phthalocyanines on contrary to a reduced conductivity in hexyl substituted one. An optical band shift of the C8LuPc2 and C8GdPc2 thin films occurred on oxidation by bromine vapour. Oxidations of Pc-coated ITO were also achieved by applying potential at 0.88 V and 0.96 V electrochemically for the C8LuPc2 and C8GdPc2 compounds, respectively. To explore the applications of these compounds in biosensing, in situ interaction studies between bromine oxidised compounds and biological cofactors nicotinamide adenine dinucleotide (NADH) and L-ascorbic acid (vitamin C) were carried out using optical absorption spectroscopy. Thin films of a non-peripherally octyl substituted LC lead phthalocyanine was exposed to 99.9 % pure hydrogen sulfide gas to produce hybrid nanocomposites consisting of lead sulphide quantum dots embedded in the analogous metal free phthalocyanine matrix. Trapping of charge carriers caused hysteresis in the current-voltage characteristics of the film on interdigitated gold electrodes. The charge hopping distance was found to be 9.05 nm, more than the percolation limit and responsible for forming two well-defined conducting states with potential application as a memristor.

This report describes an experimental study of the conduction and absorption mechanisms of Germanium in the temperature range 4.2 - 1.5 K. The results of these studies were mainly devoted to the developments of very far infrared detectors. Germanium (Ge) is a well-known semiconductor element used widely, when doped with small concentration of impurities, for detection of far infrared wavelengths up to 100~m. For doping concentrations less 16 3 than 1.0 x 10 atoms/em, the absorption of radiation in the range 100- 1000~m is very weak Because of the lack of the proper absorption mechanisms, except for some photo-hopping absorption in compensated samples around 1000llm.16 -3 In the range of doping between 1-8 x 10 cm ,there exists additional thermal activation energy not present in the lower concentrations. It was thought that this activation energy results from impurity interactions in this doping range, and hence a delocalized energy band is thus formed above the ground state level. However, the electrical conduction, the width of this band and its position, and the relevance of this band to the marked bolometric effect for 10o-lOOOWU wavelength detections are not yet clear. This thesis presents further study on this band together with its relation to the conduction and absorption mechanisms. Comparative studies were usually made for two samples of Ge differing in doping configuration, one of which does not have this additional activation energy (low concentration) . The firs two chapters give a review of the absorption and conduction mechanisms in Ge at low temperatures, and the performance relations and measurements for different types of infrared detectors. In this report, the conduction mechanism is studied for the two samples, and includes galvanometric properties, thermal properties and energy scattering processes for the carriers in the delocalized band. The absorption characteristics, 1n lOO-lOOO~ru range of the two samples were investigated. Germanium elements with absorbing surfaces are also studied using two different techniques, namely, surface ion implantation and metal film deposition. The mutual effects of the implanted surface and the bulk material are discussed and suggestions for the future of this technique are given. Finally, the design and performance of the constructed high sensitivity far infrared Ge detectors using the higher concentration sample are given. Theoretical noise limitations were reached in these detectors. Heasurements and practicaI. astronomical applications are also given.

En la presente tesis doctoral se ha realizado un estudio computacional de las propiedades electrónicas de sistemas basados en cadenas metálicas monodimensionales de la familia de los llamados nanowires, concretamente su magnetismo y conductividad. Estas cadenas lineales se sustentan gracias a los ligandos orgánicos que se organizan a su alrededor, cuyo número de sitios de unión determina la nuclearidad de la cadena. Para estas moléculas, llamadas cadenas metálicas extendidas, se han calculado los parámetros de acoplamiento magnético con el método CASPT2. El uso del Hamiltoniano de Heisenberg estándar para los sistemas M3(dpa)4Cl2 cuando hay dos electrones no desapareados en cada centro, ha sido examinado mediante el cálculo del valor de λ mediante cálculos DFT. Las diferentes conductividades eléctricas observadas en las cadenas MMX [Ni2(dta)4I]∞ y [Pt2(dta)4I]∞ (dta = CH3CS2) y sus estados de ordenación de carga han sido analizados con parámetros de estructura electrónica extraídos a partir de cálculos DFT periódicos y de correlación combinados con la teoría del Hamiltoniano efectivo. / In the present thesis, magnetic and conducting properties of systems, one-dimensional chains of the family of so-called nanowires, have been studied computationally. These linear chains are supported by organic ligands surrounding the metal backbone where the number of binding sites determines the nuclearity of the chain. For these molecules, also called extended metal atom chains, magnetic coupling parameters have been calculated with the CASPT2 method. The use of standard Heisenberg Hamiltonian for systems M3(dpa)4Cl2 when two unpaired electrons are localized on each magnetic center has been examined by calculating the value of λ from DFT calculations. The different electrical conductivities observed in MMX chains [Ni2(dta)4I]∞ and [Pt2(dta)4I]∞ (dta = CH3CS2) and the charge ordering state have been analyzed with DFT periodic calculations and also through the comparison of extracted electronic structure parameters from ab initio calculations combined with the effective Hamiltonian theory.

Per paskutinį dešimtmetį anglies nanostuktūros – amorfinės anglies plėvelės, fulerenai, o ypač nanovamzdeliai patraukė daugelio tyrėjų dėmesį. Šios struktūros yra daug žadančios puslaidininkių pramonėje, dėl galimybių prietaisų miniatiūrizavimui. Šiuo metu nanotechnologija patraukia vis didesnį dėmesį. Neabejojama anglies ir kitų nanostruktūrų išskirtinėmis savybėmis ir bandoma jas pritaikyti įvairiose srityse, tačiau šių struktūrų įdiegimą riboja tai, kad sunku pagaminti norimų struktūrų ir išmatavimų anglies nanodarinius, nes būtent anglies nanodarinių struktūra nulemia šių darinių fizikines savybes, taipogi ir laidumą. / Carbon nanodivices have attracted the attention of many researchers since their discovery last decade. These carbon molecules are tiny tubes with diameters down to 0.4 nm, while their lengths can grow up to a million times their diameter. Using their remarkable electrical properties, simple electronic logic circuits have been built. These structures are promising for the semiconductor industry which is leading the search of miniaturization. They are not only very good conductors, but they also appear to be the yet found material with the biggest specific stiffness, having half the density of aluminium. They also have great active surface. The aim of this work is to analyse the variable range hopping ( VRH ) conduction, which can describe conduction mechanism in carbon films. Also, to find conduction parameters, whish describe the conduction mechanism in carbon films and carbon nanotubes networks. In that work was analysed impacts of photon – assisted tunneling on electrical conductivity in carbon nanotubes networks mechanism.

No description available.

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.

Made available in DSpace on 2016-06-02T20:15:32Z (GMT). No. of bitstreams: 1 5887.pdf: 17427536 bytes, checksum: 86a72410b26eb5474b5d0a693e193449 (MD5) Previous issue date: 2013-12-19 / Financiadora de Estudos e Projetos / Multiferroic are materials which have at least two of the three ferroics orders: ferromagnetism, ferroelectricity and/or ferroelasticity. The coupling between these properties, make multiferroic materials of great technological and scientific interest, mainly in the design of new devices such as sensors and spintronic devices. The lead iron tungstate Pb(Fe2=3W1=3)O3 (PFW) is a relaxor multiferroic with ferroelectric transition TC ~ 180K and antiferromagnetic TN ~ 340K, it is a member of the relaxor ferroelectrics family with perovskite structure, in which the two types of cations (Fe3+ e W6+) are randomly distributed in the B site, causing the formation of polar nanoregions (or clusters) of order/disorder at microscopic scale, which would be the origin of the relaxor behavior. Lead iron niobate Pb(Fe1=2Nb1=2)O3 (PFN) is a ferroelectric with diffuse phase transition (DPT) around TC ~ 380K and antiferromagnetic, with the G-type ordering below the Néel temperature, reported in TN ~ 143K. This material has a high dielectric constant, and excellent ferroelectric properties. The Pb2+, at site A, and Nb5+, at site B are responsible for the ferroelectric order, as the Fe3+ at site B is responsible to provide the necessary magnetic moment for the magnetic ordering. In this work, the electrical conduction and relaxation mechanism of multiferroics PFW and PFN ceramics were investigated. The PFW and PFN samples were prepared by solid state reaction method through two stages. This method was effective to obtain samples with majoritary perovskite phase (95,6% and 95,7%), respectively. After the densification process through sintering methods used in this work (conventional sintering, hot pressing and spark plasma), the perovskite phase was increased, being almost 100 %. The samples of PFW and PFN obtained by the different densification techniques, were dense and practically free of pores. For the analysis of the dielectric response of the samples, it was proposed in this work, an analysis protocol, which was effective to find the responsible mechanisms for the dielectric response of the studied materials. Two relaxation processes were identified for each studied sample, which were labeled as: PR-1, PR-2 or PR *. These processes can be attributed to the interfacial polarization and polarization by hopping, occurring due to the presence of defects in the lattice, such as the oxygen vacancies and lead vacancies. From the dependence of the DC electrical conductivity versus temperature, it was possible to identify regions with different mechanisms of electrical conduction for the samples of PFW and PFN. These mechanisms are, thermally activated at high temperatures, hopping of small polarons at intermediate temperatures and variable range hopping at low temperatures. / Multiferróicos são materiais que têm pelo menos duas das três ordens ferróicas: ferromagnetismo, ferroeletricidade e/ou ferroelasticidade. O acoplamento entre essas propriedades, faz com que os materiais multiferróicos despertem um grande interesse científico e tecnológico, principalmente na concepção de novos dispositivos, como sensores e dispositivos de spintrônica. O tungstanato de ferro e chumbo Pb(Fe2=3W1=3)O3 (PFW) é um multiferróico relaxor com transição ferroelétrica TC ~ 180K e antiferromagnética TN ~ 340K, ele é membro da família dos ferroelétricos relaxores com uma estrutura perovskita, em que os dois tipos de cátions (Fe3+ e W6+) são aleatoriamente distribuídos no sítio B, fazendo com que em escala microscópica existam nanoregiões polares (ou clusters) de ordem/desordem neste sítio, que seriam a origem do comportamento relaxor. O niobato de ferro e chumbo Pb(Fe1=2Nb1=2)O3 (PFN) é um ferroelétrico com transição de fase difusa (TFD) ao redor de TC ~ 380K, e antiferromagnético, com ordenamento do tipo-G abaixo da temperatura de Néel reportada em TN ~ 143K. Ele ainda apresenta uma alta constante dielétrica, além de excelentes propriedades ferroelétricas. Neste material o Pb2+, no sítio A, e Nb5+, no sítio B são responsáveis pelo ordenamento ferroelétrico, enquanto o Fe3+ no sítio B é responsável em fornecer o momento magnético necessário para o ordenamento magnético. Neste trabalho, os mecanismos de condução e relaxação elétrica das cerâmicas multiferróicas de PFW e PFN foram investigados. As amostras de PFW e PFN foram preparadas por reação de estado sólido através do método de dois estágios, que se mostrou eficaz na obtenção de amostras com fase perovskita majoritaria (95,6% e 95,7%), respectivamente. De modo geral, essas amostras ao passar pelo processo de densificação através dos métodos de sinterização utilizados nesse trabalho (sinterização convencional, sinterização por prensagem uniaxial a quente e sinterização por spark plasma), tiveram suas fases perovskitas majoritarias aumentadas, chegando à praticamente 100%. As amostras de PFW e PFN, obtidas pelas diferentes técnicas de densificação, mostraram-se densas e praticamente livres de poros. Para análise da resposta dielétrica apresentada por essas amostras, foi proposto neste trabalho um protocolo de análise, que se mostrou eficaz em descrever o comportamento da resposta dielétrica apresentado pelas mesmas. Foram identificados dois processos de relaxação para cada amostra em estudo, os quais foram identificados por: PR-1, PR-2 ou PR*. Esses processos podem ser atribuídos à polarização interfacial e à polarização por salto, os quais ocorrem pela presença de defeitos na rede, tais como, as vacâncias de oxigênio e as vacâncias de chumbo. Através da dependência da condutividade elétrica DC em função da temperatura, foi possível identificar regiões com diferentes mecanismos de condução para as amostras de PFW e PFN. Dentre eles estão, ativação térmica em altas temperaturas, hopping de pequenos polarons em temperaturas intermediárias e hopping de alcance variável em baixas temperaturas.

Ternary chalcopyrite compounds are the semiconductors with suitable properties to be used as absorber materials in thin film solar cells. AgInSe2 is a promising candidate with its several advantages over the widely used CuInSe2. The purpose of this study was to optimize the physical properties of the Ag-In-Se (AIS) thin films that were deposited by e-beam evaporation of Ag3In5Se9 single crystal powder for solar cell applications by means of post-annealing process under nitrogen atmosphere. The as-grown AIS thin films were annealed at 200, 300 and 400oC and their structural, optical, electrical and photoelectrical properties were examined to observe the effects of post-annealing process. Structural characterization of the films was performed by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) analyses. Optical properties of the films were investigated by optical transmittance measurements. Electrical and photoelectrical properties of the films were examined by temperature dependent conductivity, photoconductivity under different illumination intensities and spectral photoresponse measurements. It was discovered that the annealing of AIS thin films at 200oC resulted in the best physical properties for solar cell applications. The obtained films were polycrystalline with mixed binary and ternary crystalline phases, such as Ag3In5Se9, AgInSe2 and InSe, and showed n-type conductivity with room temperature conductivity value of 2.3x10-6 (Ohm&shy / cm)-1. The band gap energy of the 200oC-annealed films was determined as 1.68 eV from spectral photoresponse measurements. The results of the study revealed that the inadequate Ag incorporation and segregation and/or reevaporation of Se atoms at high annealing temperatures were the major problems encountered in producing single phase polycrystalline AgInSe2 thin films. The required stoichiometry of thin films should be maintained during the growth of the films by means of an alternative deposition procedure and the films should be selenized during post-annealing process.

Un « Nanonet », acronyme pour « NANOstructured NETwork », est défini comme un réseau de nanostructures unidimensionnelles à fort facteur de forme et aléatoirement orientées sur un substrat. Dans ce travail de thèse, une étude approfondie de nanonets à base de nanofils de silicium est présentée en vue d'une intégration dans des capteurs d'ADN. Une méthode de fabrication simple de ces réseaux a tout été d'abord développée afin d'obtenir des nanonets homogènes et reproductibles. La surface des nanofils a ensuite été fonctionnalisée afin de permettre la détection de l'hybridation de l'ADN par fluorescence. Les capteurs ainsi réalisés présentent une excellente sélectivité et une meilleure limite de sensibilité que des substrats plans. Les propriétés électriques des nanonets de silicium ont également été étudiées ce qui a mené à la description des mécanismes de conduction de ces réseaux. Ainsi, il a été démontré que le comportement électrique de ces structures est dominé par les nombreuses jonctions nanofil-nanofil et suit la théorie de la percolation électrique. De plus, une procédure d'optimisation de ces jonctions a finalement permis de stabiliser les propriétés électriques des nanonets de silicium.Ces réseaux possèdent donc des propriétés remarquables provenant des constituants individuels, les nanofils, qui présentent une surface spécifique élevée, mais également de leur structure en réseaux aléatoires offrant la possibilité de les manipuler simplement et à bas coût à l'échelle macroscopique. Ces travaux ouvrent la voie à l'intégration des nanonets de silicium dans des capteurs d'ADN reposant sur la détection électrique. / A "nanonet", acronym for "NANOstructured NETwork", is defined as a network of one-dimensional nanostructures with high aspect ratio and randomly oriented on a substrate. In this work, a comprehensive study of nanonets based on silicon nanowires is presented for integration into DNA sensors. First, a simple method for the network fabrication has been developed in order to obtain homogeneous and reproducible nanonets. Then, the nanowire surface has been functionalized, so that the DNA hybridization detection is possible by fluorescence. The elaborated sensors exhibit excellent selectivity and a better sensitivity limit than planar substrates. The electrical properties of the silicon nanonets have also been investigated which resulted in the description of the conduction mechanisms of these networks. It has been shown that the electrical behaviour of such structures is ruled by the numerous nanowire-nanowire junctions and follows the electrical percolation theory. Moreover, an optimization procedure of these junctions has allowed stabilizing the electrical properties of silicon nanonets.Therefore, these networks have attractive characteristics which arise from the individual components, the nanowires with a high specific surface, but also from the structural properties of the network itself which can be simply manipulated, at a low cost, on macroscopic scales. This work paves the way for the integration of silicon nanonets into DNA sensors based on electrical detection.

Made available in DSpace on 2018-06-27T19:13:32Z (GMT). No. of bitstreams: 3 Renato Fumagalli Miranda.pdf: 2985901 bytes, checksum: f813463dac4d793c0857ee6b4b4edde1 (MD5) Renato Fumagalli Miranda.pdf.txt: 143222 bytes, checksum: 4e66988cfb8dbe77f967d7b19c2e2ce9 (MD5) Renato Fumagalli Miranda.pdf.jpg: 3661 bytes, checksum: 7c493ae73dcaa2a6a45615b6623fec9b (MD5) Previous issue date: 2010-12-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this work is described the development and application of a didactic activity of teaching that uses an analogy and Modellus software to assist in learning the concepts involved in the microscopic theory of electrical conduction. This work uses as a theoretical basis the theory of Meaningful Learning of David Ausubel and modeling Schematic proposed by Ibrahim A. Halloun. The use of analogies is modeled on TWA -Teaching-With-Analogies developed by Glynn by and modified Harrison and Treagust. To represent the microscopic theory of electrical conduction was used a mechanical analogy proposed by Bagnato and Rodrigues and adapted by Orengo. During the implementation of this activity the students were very interested and motivated to participate. In a qualitative analysis of the results is evidence that most students achieved learning significant. / Neste trabalho está descrito o desenvolvimento e aplicação de uma atividade didática de ensino que utiliza analogia e o software Modellus para auxiliar na aprendizagem dos conceitos envolvidos na teoria microscópica da condução elétrica. Este trabalhou utiliza como fundamentação teórica a Teoria da Aprendizagem Significativa de David Ausubel e a modelagem esquemática proposta por Ibrahim A. Halloun. A utilização de analogias segue o modelo TWA - Teaching-With-Analogies (ensinando com analogias) desenvolvido por Glynn e modificado por Harrison e Treagust. Como situação análoga a teoria microscópica da condução elétrica foi utilizado o análogo mecânico proposto por Bagnato e Rodrigues e adaptado por Orengo. Durante a aplicação desta atividade os alunos mostraram-se bastante interessados e motivados a participar. Analisando qualitativamente os resultados da aplicação há indícios que a maioria dos alunos atingiu uma aprendizagem significativa.