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Made available in DSpace on 2018-11-26T17:42:25Z (GMT). No. of bitstreams: 0 Previous issue date: 2017-12-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) This paper describes a new statistical model to predict the frequency dependence of the conductivity of conjugated polymer-semiconductor nanoparticle composites. The model considers AC conduction in an inhomogeneous medium represented by a two-dimensional model of resistor network. The conductivity between two neighboring sites in the polymer matrix and the semiconductor particles is assumed to obey the random free energy barrier model and the Drude model, respectively. The real and imaginary parts of the AC conductivity were determined using the transfer-matrix technique, and the statistical model was applied to experimental data of thin films composed of polyaniline (PANI) and indium-tin-oxide (ITO) nanoparticles. The conductivity critical exponent (s) obtained in two dimensions for PANI/ITO films below the percolation threshold was found to be 2.7, which is greater than the universal value of s described by the classical percolation theory (s = 1.3). This non-universality is explained by the existence of a local electric field distribution in the bulk of the nanocomposite. Finally, these results are discussed in terms of the distribution of potential barriers that vary according to the concentration of ITO amount in the composite. Univ Sao Paulo, Inst Fis Sao Carlos, BR-13560970 Sao Carlos, SP, Brazil IFMG, Campus Ouro Preto, BR-35400000 Ouro Preto, MG, Brazil Univ Fed Ouro Preto, Dept Fis, BR-35400000 Ouro Preto, MG, Brazil Univ Estadual Paulista, Dept Fis & Quim, Campus Ilha Solteira, BR-15385000 Ilha Solteira, SP, Brazil Univ Estadual Paulista, Dept Fis & Quim, Campus Ilha Solteira, BR-15385000 Ilha Solteira, SP, Brazil

A report is made of Langmuir film of a new semi-amphiphilic alternating N-hexylpyrrole-thiophene AB copolymer (PHPT) that is amenable to transfer as Langmuir–Blodgett (LB) films. PHPT was synthesized by condensation copolymerization via Stille coupling between N-hexyl-2,5-bis(trimethylstannyl)pyrrole and 2,5-dibromothiophene in the presence of Pd(PPh3)2Cl2 as a catalyst in dry DMF and characterized with various analytical techniques. In contrast to homopolymers (e.g. poly(N-alkylpyrrole)s and poly(3-alkylthiophene)s), PHPT formed a reasonably stable monolayer, as inferred through surface pressure and surface potential isotherms, and Brewster angle microscopy (BAM). The dependence of monolayer characteristics on the spreading volume, subphase temperature and compression speeds was also investigated. Electrical characterization revealed the possibility of using PHPT LB films as gas sensors.

This paper presents a methodology for the preparation of a-HgI2 by Physical Vapor Transport and of PbI2 crystals using the Bridgman technique. The results of the growth of HgI2 diluted in PbI2 by the Bridgman technique are shown for the first time, its limit of solubility having been determined at 600 ppm of HgI2 in the PbI2 matrix. Optical absorption, photoluminescence and electrical conductivity measurements show that the crystals prepared are of good crystalline quality.

The control of the photo degradation of a fluorene–vinylene–phenylene based-polymer, poly(9,9-di-hexylfluorenediylvinylene- alt -1,4-phenylenevinylene) (LaPPS16) was achieved by addition of a radical scavenger (RS) (enhancing photo resistance) or a radical initiator (RI) (reducing photo resistance). Photoluminescence, UV–Vis absorption, 1 H NMR spectroscopies and gel permeation chromatography (GPC) revealed that the incorporating small amounts of RS or RI is an efficient way to control the rates of the photo-oxidation reactions, and thus to obtain the conjugated polymer with foreseeable degradation rates for applications in blue-light sensitive detectors for neonatal phototherapy.

In this paper, we report our experimental design in searching a smart and easy-to-read dosimeter used to detect 6MV X-rays for improving patient safety in radiation oncology. The device was based on an organic emissive solutions of poly(2-methoxy-5(2′-ethylhexyloxy)- p -phenylenevinylene) (MEH-PPV), aluminum-tris-(8-hydroxyquinoline) (Alq 3 ) and additive components which were characterized by UV–Vis absorption, photoluminescence and CIE color coordinate diagram. The optical properties of MEH-PPV/Alq 3 solutions have been examined as function of radiation dose over the range of 0–100Gy. It has shown that MEH-PPV/Alq 3 solutions are specifically sensitive to X-rays, since the effect of radiation on this organic system is strongly correlated with the efficient spectral overlap between Alq 3 emission and the absorption of degraded MEH-PPV, which alters the color and photoemission of MEH-PPV/Alq 3 mixtures from red to yellow, and then to green. The rate of this change is more sensitive when MEH-PPV/Alq 3 is irradiated in the presence of benzoyl peroxide than when in the presence of hindered phenolic stabilizers, respectively, an accelerator and an inhibitor to activate or inhibit free radical formation. This gives rise to optimize the response curve of the dosimeter. It is clear from the experimental results that organic emissive semiconductors have potential to be used as dedicated and low-cost dosimeters to provide an independent check of beam output of a linear accelerator and therefore to give patients the opportunity to have information on the dose prescription or equipment-related problems a few minutes before being exposed to radiation.

A novel approach for studying the thermal conversion of poly-p-xylylidene tetrahydrothiophenium chloride (PTHT) into poly(p-phenylenevinylene) (PPV) films has been proposed on the basis of calculated optical parameters. Spin-cast PTHT films were thermally converted into partially conjugated PPV films over conversion temperatures ranging from 22 °C to 200 °C. A strong correlation between refractive index (n) and damping constant extinction coefficient (k) was verified by spectroscopic ellipsometry (SE) for the films studied in the visible range of energy. The conversion temperature has a strong influence on the values of n and k, which were theoretically modeled using a Lorentz harmonic oscillator analysis. The films were also studied by spectroscopic techniques (photoluminescence, FTIR, and UV–VIS), and it was verified that the values of n decrease with increasing the amount of C C groups present along the polymer chains, as a strong evidence that both structure and optical properties of thermally converted PPV films can be directly compared. The optical properties of the PPV films were also compared with those of two electroluminescent derivatives in which side chains are introduced into the phenyl ring of PPV, poly(2-methoxy-5-hexyloxy)-p-phenylenevinylene) (MH-PPV) and poly(3-methoxy-5-dodecyloxy-p-phenylene–vinylene) (MD-PPV).

Neste trabalho são apresentadas a fabricação e a caracterização óptica de um novo detector de raios X para monitoramento da dose nos processos de radioterapia empregando fótons de alta energia (6,0 MV). O dispositivo foi fabricado a partir de materiais orgânicos luminescentes consolidados como elemento ativo de displays eletroluminescentes nanoestrurados, mas que, até esse momento, têm sido pouco investigados como detectores de radiação ionizante. Para tanto, foram preparadas soluções à base de tris(8-hidroxiquinolato) de alumínio - Alq3 e poli(2-metóxi-5-(2-etilhexiloxi)-pfenilenovinileno) – MEH-PPV, cujo espectro de emissão do primeiro material se sobrepõe ao de absorção do segundo. Os resultados obtidos mostram que os espectros de emissão do sistema MEH-PPV/Alq3 desloca-se do vermelho-laranja (λmax = 598 nm) para o verde (λmax = 545 nm) quando a dose de radiação vai de 0 a 100 Gy. Essa mudança, consequência da degradação induzida pela radiação do MEH-PPV, foi usada no desenvolvimento de dosímetros para possível futura aplicação no controle do tratamento de pacientes oncológicos. In this work it is presented the characterization and fabrication of a novel ionizing radiation detector for high energy photon beam (6.0 MV). It is used organic luminescent materials usually applied in light-emitting and nanostructure device, but still few explored in radiation dosimetry. Organic solutions of tris(8-hydroxyquinolinato) aluminum - Alq3 and poly[2-methoxy-5-(2’-ethylhexyloxy)-p-phenylene vinylene] - MEH-PPV were prepared to better study the impact of spectral overlap between the Alq3 emission and MEH-PPV absorption. It is observed a blue-shift on the photoluminescence of the MEH-PPV/Alq3 solution system from red-orange (λmax = 598 nm) to green (λmax = 545 nm) when the radiation dose changes from 0 to 100 Gy. This effect is attributed to the photoxidation process of MEH-PPV and was employed to design dose accumulation detector in order to represent easily the radiation dose for cancer treatment.

We report on the design, fabrication and performance of a poly (2-methoxy-5(2_-ethylhexyloxy)- p-phenylenevinylene)/tris-(8-hydroxyquinoline)aluminum (MEH-PPV/Alq3) X-ray dose detector for improving safety for cancer patients shortly before radiation therapy. The detector consists of an inexpen-sive (

We report on the investigations about the modification of optical properties induced by X-rays onto film detectors of cadmium tungstate (CdWO4), poly[2-methoxy-5(2′-ethylhexyloxy)-p-phenylenevinylene] (MEH-PPV) and polystyrene (PS) This device takes advantage of reduction of spectral overlap between the radioluminescence (RL) of CdWO4 and the absorption of MEH-PPV as it is exposed to radiation, forming the basis of a new dosimeter that is capable of converting the orange-red radioluminescence of PS:MEH-PPV:CdWO4 into green. We propose an explanation of the optical processes occurring in MEH-PPV:CdWO4 in terms of the radiation hardness of CdWO4 combined to the RL-induced degradation of MEH-PPV.

A fototerapia com luz azul (460 nm - 490 nm) é o procedimento mais utilizado para o tratamento da icterícia em recém-nascidos. Contudo, dois fatores alteraram drasticamente a eficiência desse tratamento: (1) o espectro da fonte luminosa e (2) a dose de radiação absorvida pelos neonatos. Este trabalho apresenta o desenvolvimento de detectores de radiação orgânicos e flexíveis, de baixo custo, de bom desempenho e de fácil operação para monitoramento da radiação incidente em neonatos ictéricos sob tratamento fototerápico. O princípio de funcionamento dos dispositivos baseia-se na resposta óptica de filmes finos à base de dois materiais orgânicos luminescentes: o tris (8-hidroxiquinolinato de alumínio) - Alq3 e o poli[2-metóxi-5-(2’-etilóxi)-p-fenilenovinileno] - MEH-PPV, dispersos em matriz de poliestireno – PS sob efeito de luz azul. Os resultados obtidos mostram que a radiação atua no sentido de alterar a intensidade de máxima emissão do vermelho ao verde, passando pelo amarelo, dos filmes de PS/MEH-PPV/Alq3. Esse resultado é atribuído à fotodegradação do MEH-PPV e, consequentemente, as mudanças na sobreposição entre os espectros de emissão do Alq3 e de absorção desse polímero. A resposta óptica dos filmes com a radiação foi usada para fabricar um sensor orgânico flexível, inédito e de custo inferior a R$ 0,50, para controle das condições de exposição de neonatos ictéricos à fototerapia com luz azul. Blue-light therapy (460 nm - 490 nm) is the most common treatment of jaundice in newborns. However, the efficiency of this treatment is dependent of two factors: (1) the spectrum of light source and (2) the delivered dose to the neonates. This work presents the development of a low-cost, flexible, good performance and an easy detector operation based on organic materials for evaluation of radiation dose delivered by the phototherapy units to jaundice newborns. The operation principles of the device is based on the optical response of poly [2-methoxy-5-(2’-ethylhexyloxy)-p-phenylene - MEH-PPV, tris (8-hydroxyquinolinato aluminum)-Alq3 and polystyrene-PS thin films under the effects of blue-light. It is observed that the optical response of the PS/MEH-PPV/Alq3 films changes from red to yellow, and then to green with the radiation exposure. It is attributed to the photodegradation process of MEH-PPV and also to the spectral overlap between the photoemission of Alq3 and the absorption of MEH-PPV. The optical response of PS/MEH-PPV/Alq3 films was used to develop a novel organic flexible and low cost (

Luminescent polymers are commonly employed in light-emitting displays because of their good processability and higher luminance with low power consumption. However, even though they are candidates for lighting applications, they are susceptible to photoxidation processes which dramatically change their colour with light exposure. In this work we use the light instability of luminescent polymers in order to design a blue-light dosimeter which indicates dose accumulation by multicoloured changes of photodegraded poly(2-methoxy-5(2′-ethylhexyloxy)- p -phenylenevinylene) (MEH-PPV). Photoluminescence and absorbance spectra measurements were carried out on MEH-PPV solutions under the effect of blue-light provided by phototherapy systems. All measurements were done maintaining chief conditions of jaundice treatments. It is observed that changes from orange-red to yellow clearly on colour solutions, while its peak position emission shifts from orange-red to blue and decreases in intensity with increasing radiation exposure time. Experiments performed with oxygen enriched solutions were shown to improve these effects, which is mainly caused by the competition between two possible mechanisms: a light induced polymerization of MEH-PPV and replacement of C C by C O bonds on the polymer backbone. Analyses of the relation between the irradiance produced by phototherapy systems and CIE (1931) chromatic diagram of MEH-PPV reveal this polymer as an easy to operate blue-light dosimeter, and the results reported here clearly demonstrated the possibility to produce self-adhesive patch of luminescent polymers in order to attach such organic dosimeter safety and placed closer to the skin of jaundiced infants.

In this work we investigated the effect of visible radiation on the electrical properties of poly[(2-methoxy-5-hexyloxy)-p-phenylenevinylene]- MH-PPV films and light emitting diodes. Complex impedance measurements of (Au or ITO)/MH-PPV/(Au or Al) samples were carried out at room temperature and exposed to white light. Over the frequency range from 100 mHz to 2 MHz, the electrical results of Au/MH-PPV/Au was dominated by the Cole-Cole approach, where the electrode influence is negligible. However, some additional influence of the interface was observed to occur when Al was used as electrode. These effects were observed under both dark and visible-light illumination conditions. A simple model based on resistor-capacitor parallel circuits was developed to represent the complex impedance of the samples, thereby separating bulk and interface contributions. We observed that the polymer electrical resistivity decreased while the dielectric constant of the polymer and the thickness of the Al/MH-PPV layer were almost constant with increasing light intensity. The decrease of the polymer layer resistance comes from a better charge injection due to a light induced dissociation of positive charge carriers at the electrode.

The alternating conductivity, σ *( f ) = σ ′( f ) + iσ ″( f ), of in situ polymerized polyaniline thin films doped with hydrochloric acid, deposited on top of an interdigitated gold line array previously deposited on glass substrates, were measured in the frequency ( f ) range between 0.1 Hz to 10 MHz and in the temperature range from 100 to 430 K. The results for σ ′( f ) are typical of a disordered solid material: for frequencies lower than a certain hopping frequency γ hop , log[ σ ′( f )] is frequency-independent rising almost linearly for in log f > γ hop . A master curve was thus obtained by plotting the real component of the conductivity using normalized scales σ ′( f )/ σ dc and f / γ hop , which is indicative of a single process operating in the whole frequency range. An expression encompassing the conduction through a disordered structure taken from previous random free energy barrier model for hopping carriers, as well a dielectric function to represent the capacitive behavior of the PAni was employed to fit the experimental results. The dielectric constant and activation energy for hopping carriers were obtained as function of the polymer doping level.

Complex impedance measurements were used to analyze the influence of ultraviolet and ozone gas on the electronic behaviour of ZnO films grown by rf magnetron sputtering. The data show that UV exposure strongly increases the ac conductivity of the film at very low frequencies, and that after ozone exposure it recovers the original value. At high frequencies, however, UV-light exposure it does not change the conductivity but the ozone acts in the sense to decrease it. Two distinct mechanisms, related to two relaxation time distributions are clearly observed: they are superimposed in the virgin sample, but they split forming two semicircles in the z ″( f ) − z ′( f ) diagrams when the samples are treated with UV and/or ozone gas. A combination of the bruggeman effective medium approximation (BEMA) with the random free energy barrier model is used to fit the data and to explain the ac conductivity variation phenomena observed.

Photogenerated charge carrier profiles in poly(2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene) (MEH-PPV) light-emitting diodes were determined from steady-state photocurrent spectra and transient photocurrent decay measurements. The observation that the photocurrent spectra behavior is strongly dependent on the bias polarity and amplitude suggests the existence of an intrinsic electric field, determined by the difference in the work function of the metallic electrodes, as well as a field dependence on the free charge carrier generation rates. The obtained results reveal built-in voltages of +0.2 and −0.6 V for Au and Al electrodes, respectively. The photocurrent spectra can be semi-quantitatively explained using a simple model which takes into account the internal built-in electric field of the device structure, the band gap energy and the migration/diffusion of the photogenerated charge carriers through the polymeric film. The drift mobility of carriers was investigated by the time-of-flight technique (TOF). The value for the mobility of holes was obtained from the change of slopes in the double logarithmic plot of the transient current and was independent of the applied field. The TOF transients for electrons showed no change of slopes in the double logarithmic plot and the drift mobility of electrons could not be calculated.

Organic bioelectronics is a fast-rising research field that takes advantage of the soft and conducting/semiconducting nature of conjugated polymers to create devices that communicate, interface and mimic biological systems. Bioelectronics encompasses many applications, including tissue engineering, neural interfaces and biosensors. A device that has been extensively explored for such applications is the organic electrochemical transistor (OECT). The main reason is due to its amplification nature and, thus, high fidelity transducer of biological events. Additionally, OECTs convert ionic signals to electronic ones, providing a direct link between biological ion fluxes and electronics. Even though they have been widely explored in the past 10 years, a major drawback that remains unsolved is the lack of hydrophilic polymers that are suitable for applications in biological environment. Hence, in the first part of this dissertation, we propose a novel and universal OECT architecture that enables the use of virtually any type of conjugated polymer. Using the proposed method, which was based on physical chemistry principles, we successfully fabricated transistors that exhibits very high transconductance, good stability and reproducibility, using traditional water-insoluble conjugated polymers. In the second part, we developed a biosensing application using the proposed architecture. In short, the OECT device was functionalized with a cellular membrane model, making it possible to gather quantitative data on the physical and chemical properties of the membrane. This is particularly useful for understanding how different compounds interact with cells. Additionally, we were able to study the working mechanism of lidocaine, a widely used local anesthetic. The concept presented here was then successfully extended to the fabrication of biosensors, enabling thousands of water-insoluble materials that have been developed over the last several decades to be used in organic bioelectronics devices. A bioeletrônica orgânica é um campo de pesquisa que cresce rapidamente. Se beneficiando da natureza condutora/semicondutora e flexível dos polímeros conjugados, seu principal objetivo é o desenvolvimento de dispositivos eletrônicos capazes de interfacear, mimetizar e se comunicar com sistemas biológicos. A bioeletrônica envolve diversos tipos de aplicações, dentre eles engenharia de tecidos, interfaces neurais e biossensores. Um dispositivo que tem sido extensivamente explorado para esses tipos de aplicações é o transistor eletroquímico orgânico (OECT). OECTs convertem correntes ionicas para eletrônicas, atuando como uma conexão direta entre fluxos iônicos, tipícos de eventos biológicos, e a eletrônica. Apesar de terem sido amplamente explorados na última década, uma de suas desvantagens que permanece sem solução é a falta de polímeros adequados para os ambientes biológicos, que devem ser hidrofílicos. Por isso, na primeira parte dessa dissertação, nós propomos uma nova arquitetura universal de OECT, que permite o uso de virtualmente qualquer tipo de polímero conjugado. Utilizando o método proposto, baseado em princípios físico-químicos, fabricamos transistores com polímeros conjugados inssoluveis em água que exibem alta trancondutancia, boa estabilidade e reproducibilidade. Em seguida, desenvolvemos uma aplicação em biossensores utilizando a arquitetura proposta. Em resumo, o OECT foi funcionalizado com um modelo de membrane celular, possibilitando a aquisição de informações quantitativas sobre propriedades físico-químicas da membrana. Isso é particularmente útil para o estudo de como diferentes compostos interagem com células. Além disso, utilizamos a plataforma para estudar o mecanismo de funcionamento da lidocaina, um anestésico local aplamente utilizado. Assim, o conceito aqui apresentado foi estendido para a fabicação de biossensores, permitindo que milhares de materiais insoluveis em água possam ser utilizados na bioeletrônica orgânica.