Dispositifs optoélectroniques à base de semi-conducteurs organiques en couches minces

Les petites molécules de type p à bandes interdites étroites sont de plus en plus perçues comme des remplaçantes possibles aux polymères semi-conducteurs actuellement utilisés conjointement avec des dérivés de fullerènes de type n, dans les cellules photovoltaïques organiques (OPV). Par contre, ces petites molécules tendent à cristalliser facilement lors de leur application en couches minces et forment difficilement des films homogènes appropriés. Des dispositifs OPV de type hétérojonction de masse ont été réalisés en ajoutant différentes espèces de polymères semi-conducteurs ou isolants, agissant comme matrices permettant de rectifier les inhomogénéités des films actifs et d’augmenter les performances des cellules photovoltaïques. Des polymères aux masses molaires spécifiques ont été synthétisés par réaction de Wittig en contrôlant précisément les ratios molaires des monomères et de la base utilisée. L’effet de la variation des masses molaires en fonction des morphologies de films minces obtenus et des performances des diodes organiques électroluminescentes reliées, a également été étudié. La microscopie électronique en transmission (MET) ou à balayage (MEB) a été employée en complément de la microscopie à force atomique (AFM) pour suivre l’évolution de la morphologie des films organiques minces. Une nouvelle méthode rapide de préparation des films pour l’imagerie MET sur substrats de silicium est également présentée et comparée à d’autres méthodes d’extraction. Motivé par le prix élevé et la rareté des métaux utilisés dans les substrats d’oxyde d’indium dopé à l’étain (ITO), le développement d’une nouvelle méthode de recyclage eco-responsable des substrats utilisés dans ces études est également présenté.

Dispositifs optoélectroniques à base de semi-conducteurs organiques en couches minces

Les petites molécules de type p à bandes interdites étroites sont de plus en plus perçues comme des remplaçantes possibles aux polymères semi-conducteurs actuellement utilisés conjointement avec des dérivés de fullerènes de type n, dans les cellules photovoltaïques organiques (OPV). Par contre, ces petites molécules tendent à cristalliser facilement lors de leur application en couches minces et forment difficilement des films homogènes appropriés. Des dispositifs OPV de type hétérojonction de masse ont été réalisés en ajoutant différentes espèces de polymères semi-conducteurs ou isolants, agissant comme matrices permettant de rectifier les inhomogénéités des films actifs et d’augmenter les performances des cellules photovoltaïques. Des polymères aux masses molaires spécifiques ont été synthétisés par réaction de Wittig en contrôlant précisément les ratios molaires des monomères et de la base utilisée. L’effet de la variation des masses molaires en fonction des morphologies de films minces obtenus et des performances des diodes organiques électroluminescentes reliées, a également été étudié. La microscopie électronique en transmission (MET) ou à balayage (MEB) a été employée en complément de la microscopie à force atomique (AFM) pour suivre l’évolution de la morphologie des films organiques minces. Une nouvelle méthode rapide de préparation des films pour l’imagerie MET sur substrats de silicium est également présentée et comparée à d’autres méthodes d’extraction. Motivé par le prix élevé et la rareté des métaux utilisés dans les substrats d’oxyde d’indium dopé à l’étain (ITO), le développement d’une nouvelle méthode de recyclage eco-responsable des substrats utilisés dans ces études est également présenté.

Análise de desempenho de redes p2p com protocolo push/pull para distribuição de vídeo na presença de nós não-cooperativos.

O uso de Internet para a distribuição de fluxos de vídeo tem se mostrado uma tendência atual e traz consigo grandes desafios. O alicerce sobre qual a Internet está fundamentada, comutação por pacotes e arquitetura cliente-servidor, não proporciona as melhores condições para este tipo de serviço. A arquitetura P2P (peer-to-peer) vem sendo considerada como infraestrutura para a distribuição de fluxos de vídeo na Internet. A idéia básica da distribuição de vídeo com o suporte de P2P é a de que os vários nós integrantes da rede sobreposta distribuem e encaminham pedaços de vídeo de forma cooperativa, dividindo as tarefas, e colocando à disposição da rede seus recursos locais. Dentro deste contexto, é importante investigar o que ocorre com a qualidade do serviço de distribuição de vídeo quando a infraestrutura provida pelas redes P2P é contaminada por nós que não estejam dispostos a cooperar, já que a base desta arquitetura é a cooperação. Neste trabalho, inicialmente é feito um estudo para verificar o quanto a presença de nós não-cooperativos pode afetar a qualidade da aplicação de distribuição de fluxo de vídeo em uma rede P2P. Com base nos resultados obtidos, é proposto um mecanismo de incentivo à cooperação para que seja garantida uma boa qualidade de vídeo aos nós cooperativos e alguma punição aos nós não-cooperativos. Os testes e avaliações foram realizados utilizando-se o simulador PeerSim.

Spiroacetals in the Colonization Behaviour of the Coffee Berry Borer: A 'Push-Pull' System

Coffee berries are known to release several volatile organic compounds, among which is the spiroacetal, conophthorin, an attractant for the coffee berry borer Hypothenemus hampei. Elucidating the effects of other spiroacetals released by coffee berries is critical to understanding their chemo-ecological roles in the host discrimination and colonization process of the coffee berry borer, and also for their potential use in the management of this pest. Here, we show that the coffee berry spiroacetals frontalin and 1,6-dioxaspiro [4.5] decane (referred thereafter as brocain), are also used as semiochemicals by the coffee berry borer for host colonization. Bioassays and chemical analyses showed that crowding coffee berry borers from 2 to 6 females per berry, reduced borer fecundity, which appeared to correlate with a decrease in the emission rates of conophthorin and frontalin over time. In contrast, the level of brocain did not vary significantly between borer-uninfested and infested berries. Brocain was attractive at lower doses, but repellent at higher doses while frontalin alone or in a blend was critical for avoidance. Field assays with a commercial attractant comprising a mixture of ethanol and methanol (1:1), combined with frontalin, confirmed the repellent effect of this compound by disrupting capture rates of H. hampei females by 77% in a coffee plantation. Overall, our results suggest that the levels of frontalin and conophthorin released by coffee berries determine the host colonization behaviour of H. hampei, possibly through a 'push-pull' system, whereby frontalin acts as the 'push' (repellent) and conophthorin acting as the 'pull' (attractant). Furthermore, our results reveal the potential use of frontalin as a repellent for management of this coffee pest.

Analysing DBD plasma lamp intensity versus power consumption using a push-pull pulsed power supply

In this paper characteristic of a DBD (Dielectric Barrier Discharge) plasma lamp is investigated based on the lamp intensity and power consumption. A pulsed power supply with controllable parameters based on a push-pull converter is developed for lamp excitation at different voltage levels and repetition rate. The experimentations were conducted for 28 different operating points with the frequency range of 2 kHz to 15 Khz at output voltage levels of between 7.4 kV up to 13 kV. The obtained results show the feasibility of finding an optimum operation point due to nonlinear behaviour of the DBD lamp.

A switching control strategy for single and dual inductor push-pull converters

A switching control strategy is proposed for single and dual inductor current-fed push-pull converters. The proposed switching control strategy can be used with both current-fed push-pull converters with an active voltage doubler rectifier, or active rectifier, in the secondary side of the isolation transformer. The proposed switching control strategy makes turn-on and turn-off processes of the primary side power switches zero-voltage-switching and zero-current-switching respectively. The soft-switching operation of the single and dual inductor push-pull converters, with both types of active rectifier, is explained. Simulation and experimental results are provided to validate soft switching operation of the current-fed push-pull converters with the proposed switching control strategy.

Soft-switching single inductor current-fed push-pull converter for PV applications

A switching control strategy is proposed for single inductor current-fed push-pull converter with a secondary side active voltage doubler rectifier or a voltage rectifier used in photovoltaic (PV) grid interfacing. The proposed switching control strategy helps to turn-on and turn-off the primary side power switches with zero-voltage and zero-current switching. The operation of the push-pull converter is analyzed for two modes of operation. The feasibility of the proposed switching control strategy is validated using simulation and experimental results.

Ferrocene in conjugation with a Fischer carbene: Synthesis, NLO, and electrochemical behavior of a novel organometallic push-pull system

Using an iterative sequence of Wittig olefination, reduction, oxidation, and condensation of an active methylene group to carbonyl, it was possible to prepare a series of organometallic push-pull molecules [(CO)(5)M=C(OCH3)(-CH=CH-)(n)(C5H4)Fe(C5H5), M = W, Cr, n = 1-4] in which ferrocene is the donor element and a Fisher carbene moeity is the acceptor group. The molecular first hyperpolarizability beta was determined by hyper-Rayleigh scattering experiments. The beta values ranged from 110 x 10(-30) to 2420 x 10(-30) esu in acetonitrile, and they are among the highest reported for organometallic molecules so far. Electrochemical measurements are consistent with the push-pull nature of these compounds.

Crystallographic study of push-pull ethylenes

From structural data of several crystal structure analyses of push-pull ethylenes it is found that C=C bond lengths in this class of molecules are significantly longer than the value for this bond in ethylene. With powerful donors and acceptors such as -NMe2 and -COOMe groups respectively, the C=C bond length is as long as 1.460 å. Correlations are observed between (i) C=C bond lengths and the twist angles about the C=C bond and (ii) C=C bond lengths and the torsional barrier measured by thednmr technique.

Push-pull ethylenes: the structures of 3-(2-imidazolidinylidene)-2,4-pentanedione (I), C8H12N2O2, and 3-(1,3-dimethyl-2-imidazolidinylidene)-2,4-pentanedione trihydrate (II), C10H16N2O2.3H2O

(I): Mr= 168, triclinic, P1, Z=2, a= 5.596 (2), b = 6.938 (3), c = 10.852 (4) A, ~t= 75.64 (3), fl= 93.44 (3), ),= 95.47 (3) °, V= 406.0A 3, Din= 1.35 (by flotation using carbon tetrachloride and n-hexane), D x= 1.374 Mg m -3, g(Mo Kct, 2 = 0.7107 A) = 1.08 cm -l, _F(000) = 180, T= 293 K. (II): Mr= 250, triclinic, P1, Z= 2, a = 7.731(2), b=8.580(2), c=11.033(3)A, a= 97-66 (2), fl= 98.86 (2), y= 101.78 (2) °, V= 697.5 A 3, D m = 1.18 (by flotation using KI solution), Dx= 1.190Mgm -3, g(MoKa, 2=0.7107A)= 1.02 cm -1, F(000) = 272, T= 293 K. Both structures were solved by direct methods and refined to R = 4.4% for 901 reflexions for (I) and 5.7% for 2001 reflexions for (II). The C=C bond distances are 1.451 (3) A in (I) and 1.468 (3)A in (II), quite significantly longer than the C=C bond in ethylene [1.336 (2).~; Bartell, Roth, Hollowell, Kuchitsu & Young (1965). J. Chem. Phys. 42, 2683-2686]. The twist angle about the C=C bond in (II) is 72.9 (5) ° but molecule (I) is essentially planar, the twist angle being only 4.9 (5) ° .

Crystal Structure, Ultraviolet Spectrum, and Electronic Structure of a Strongly Twisted Push-Pull Ethylene, approaching an Amidinium-Vinylogous Dithioate Zwitterion

The crystal structure of 1,3-di benzyl -2 - (4,4-dimet hyl- 2,5- bist hioxocyclo hexylidene) imidazolidine (2) shows a twist of 80.8(5)' about the inter-ring bond, which has a length of 1.482(6) A. The near orthogonality of the donor and acceptor parts of this formal push-pull ethylene makes the structure approach that of a zwitterion, as evidenced by bond lengths indicating strong electron delocalization. The acceptor part approaches a vinylogous dithioate structure, the donor part an amidinium system. The U.V. spectrum shows an n + R and a R + R transition, at 51 1 and 41 7.5 nm, respectively; according to CNDO/S calculations these are located entirely in the [S-C-C-C-SI- part. Two bands at shorter wavelength are ascribed to transitions from combinations of the lone-pair orbitals on the sulphur atoms to a n* orbital in the [N-C-N] + part; this is facilitated by the near perpendicularity of the two parts of the molecule.

Second harmonic generation in poled molecularly doped polymer films : Push-pull butadienes in poly(methyl methacrylate) and polystyrene

We report second harmonic generation in a new class of organic materials, namely donor-acceptor substituted all-trans butadienes doped in poly(methyl methacrylate) or polystyrene and oriented by corona poling at elevated temperatures. Second harmonic measurements were made at room temperature. The observed d33 coefficients are greater than those of potassium dihydrogen phosphate or 4-dimethylamino-4'-nitrostilbene doped in similar polymer matrices. Rotational diffusion coefficients estimated from the decay characteristics of the second harmonic intensity in the polymer films indicate that the polymer matrix plays a major role in stabilizing the dopants in a nonlinear optics conducive environment.

Spectroscopic, redox and photophysical properties of push-pull fluoroarylporphyrins

Novel fluoroarylporphyrins bearing electron donor dimethylamino groups in the meso-aryl positions and an electron acceptor nitro group on one of the pyrrole carbons exhibit significant solvent dependent fluorescence spectra and time-resolved emission properties. These effects are suggestive of intramolecular charge transfer (ICT) in the singlet excited state of these porphyrins. Electrochemical redox behaviour of these porphyrins showed the presence of substantial donor-acceptor interactions in the nitro-amino porphyrins.