Στην εργασία αυτή μελετάται η ηλεκτρική απόκριση νανοσύνθετων υλικών πολυαιθυλενοξειδίου (poly(ethylene oxide)) – τροποποιημένων νανοσωλήνων άνθρακα πολλαπλού τοιχίου (MWCNT), ως συνάρτηση της περιεκτικότητας σε νανοσωλήνες άνθρακα. Συγκεκριμένα εξετάζεται η διηλεκτρική απόκριση και η ειδική αγωγιμότητα των νανοσύνθετων με παραμέτρους την περιεκτικότητα σε MWCNT, τη θερμοκρασία και τη συχνότητα του εφαρμοζόμενου ηλεκτρικού πεδίου. Από τη διηλεκτρική απόκριση εξάγονται πληροφορίες σχετικά με την μοριακή κινητικότητα του συστήματος και διεπιφανειακά φαινόμενα. Η εξάρτηση της ειδικής αγωγιμότητας από την περιεκτικότητα σε MWCNT δίνει τη δυνατότητα προσδιορισμού του κατωφλιού μετάβασης από τη μονωτική στην αγώγιμη συμπεριφορά, ενώ η εξάρτηση της ειδικής αγωγιμότητας από τη θερμοκρασία και τη συχνότητα προσφέρει τη δυνατότητα μελέτης των μηχανισμών μεταφοράς ηλεκτρικού φορτίου. Για τον καλύτερο προσδιορισμό των μηχανισμών ηλεκτρικής αγωγής εξετάζεται η δυνατότητα περιγραφής των πειραματικών αποτελεσμάτων μέσω των θεωρητικών προσεγγίσεων Variable Range Hopping model και Symmetric Hopping model. Για λόγους αναφοράς εξετάζεται και η ηλεκτρική απόκριση του καθαρού πολυμερούς και νανοσύνθετων, της ίδιας πολυμερικής μήτρας, που περιλαμβάνουν μη τροποποιημένους νανοσωλήνες άνθρακα. Τέλος, το σύνολο των αποτελεσμάτων γίνεται αντικείμενο εκτεταμένης συζήτησης. / In the present work the electric response of nanocomposites material consisted of poly (ethylene oxide) as matrix and modified multiwall carbon nanotubes (MWCNT) as reinforcing phase, is studied. Specifically, the dielectric response and the conductivity of nanocomposites is examined with parameters the content in MWCNT, the temperature and the frequency of the applied electric field. From the dielectric response valuable information concerning the molecular mobility of the systems and the interfacial phenomena can be extracted. The dependence of conductivity on the MWCNT content allows the determination of percolation threshold or critical concentration, which governs the transition from the insulating to the conductive behaviour. Moreover, the dependence of conductivity on temperature and frequency offers the possibility of studying the occurring charge transport mechanisms. Aiming to study further the type of the conduction mechanisms, the applicability of Variable Range Hopping model and Symmetric Hopping model is tested. For reasons of reference the electric response of pure polymer matrix and nanocomposites incorporating unmodified MWCNT is also examined. Finally, results become the object of an extensive discussion.

abstract: The photosynthetic reaction center is a type of pigment-protein complex found widely in photosynthetic bacteria, algae and higher plants. Its function is to convert the energy of sunlight into a chemical form that can be used to support other life processes. The high efficiency and structural simplicity make the bacterial reaction center a paradigm for studying electron transfer in biomolecules. This thesis starts with a comparison of the primary electron transfer process in the reaction centers from the Rhodobacter shperoides bacterium and those from its thermophilic homolog, Chloroflexus aurantiacus. Different temperature dependences in the primary electron transfer were found in these two type of reaction centers. Analyses of the structural differences between these two proteins suggested that the excess surface charged amino acids as well as a larger solvent exposure area in the Chloroflexus aurantiacus reaction center could explain the different temperature depenence. The conclusion from this work is that the electrostatic interaction potentially has a major effect on the electron transfer. Inspired by these results, a single point mutant was designed for Rhodobacter shperoides reaction centers by placing an ionizable amino acid in the protein interior to perturb the dielectrics. The ionizable group in the mutation site largely deprotonated in the ground state judging from the cofactor absorption spectra as a function of pH. By contrast, a fast charge recombination assoicated with protein dielectric relaxation was observed in this mutant, suggesting the possibility that dynamic protonation/deprotonation may be taking place during the electron transfer. The fast protein dielectric relaxation occuring in this mutant complicates the electron transfer pathway and reduces the yield of electron transfer to QA. Considering the importance of the protein dielectric environment, efforts have been made in quantifying variations of the internal field during charge separation. An analysis protocol based on the Stark effect of reaction center cofactor spectra during charge separation has been developed to characterize the charge-separated radical field acting on probe chromophores. The field change, monitored by the dynamic Stark shift, correlates with, but is not identical to, the electron transfer kinetics. The dynamic Stark shift results have lead to a dynamic model for the time-dependent dielectric that is complementary to the static dielectric asymmetry observed in past steady state experiments. Taken together, the work in this thesis emphasizes the importance of protein electrostatics and its dielectric response to electron transfer. / Dissertation/Thesis / Ph.D. Physics 2012

Neste trabalho estudamos defeitos pontuais em cristais de NaCl + NaF contendo diversos íons divalentes e em especial o íon Pb++. As técnicas usadas foram as de I.T.C. e absorção ótica. Identificamos três novos defeitos e novos agregados de Pb++. Um modelo microscópico para os defeitos observados foi proposto. Dois dos novos picos de I.T.C. são identificados como relaxação do mesmo defeito constituído do íon divalente e um íon F- em sua proximidade. Pela primeira vez observou-se a conversão da relaxação dielétrica de um íon divalente isolado para a de uma posição perturbada. Os íons F- funcionam como armadilhas eficientes para a difusão do íon Pb++. O efeito do raio iônico sobre a relaxação desses defeitos foi observado e discutido. Atribuiu-se tentativamente a um par de vacâncias ao pico de I.T.C. de mais baixa temperatura / This work report results on the study of point defects in NaCl + NaF single crystals doped with several divalent ions and with more details for Pb++ ions. I.T.C. and u.v. spectroscopy were the used techniques. Three new relaxation peaks were found as well as large aggregates of Pb++ and F- ions. A microscopic model for the observed defects is proposed. Two of the new I.T.C. peaks called B and C, are identified as dielectrics relaxation of one defect - its transverse and the longitudinal relaxation modes. This defect is made of one divalent ion one F anion as its close neighbor and one vacancy. For the first time it was observed the conversion of a Pb++ ion from a normal to a perturbed lattice site. The F anions are efficient traps for divalent ion diffusion. The effect of divalent ion radius on the dielectric relaxation of these perturbed defects was observed and discussed. The lower temperature peak is tentatively attributed to relaxation of a divacancy - a pair of positive and negative vacancy bound together

Encontrou-se que a relaxação dielétrica dos dipolos impureza-vacância em KI dopado com pequenas quantidades de KCl é extremamente diferente da relaxação dielétrica na matriz KI não contendo íons Cl&#8254.Os novos picos de relaxação, atribuídos à presença do Cl&#8254 na vizinhança imediata do íon divalente, tem um tempo de relaxação 103 vezes menor que o normal na temperatura ambiente.Foi proposto um modelo para o aprisionamento dos íons divalentes pelo Cl&#8254 e estudado a influência dos raios atômicos do divalente e do anion estranho neste processo de aprisionamento. / The dielectric relaxation due to I-V dipoles in KI doped with small amounts of KCl was found to be strongly different than in KI crystals not containing Cl&#8254.The new relaxation peak attributed to the presence of the Cl&#8254 in the close neighborhood of the divalent ion has a relax¬ation time 103 greater than the normal one.A model for the trapping of the divalent ions by the Cl&#8254 is proposed. The influence of atomic radius of the divalent and the impurity anion is discussed.

Encontrou-se que a relaxação dielétrica dos dipolos impureza-vacância em KI dopado com pequenas quantidades de KCl é extremamente diferente da relaxação dielétrica na matriz KI não contendo íons Cl-. Os novos picos de relaxação, atribuídos à presença do Cl- na vizinhança imediata do íon divalente, tem um tempo de relaxação 103 vezes menor que o normal na temperatura ambiente. Foi proposto um modelo para o aprisionamento dos íons divalentes pelo Cl- e estudado a influência dos raios atômicos do divalente e do anion estranho neste processo de aprisionamento. / The dielectric relaxation due to I-V dipoles in KI doped with small amounts of KCl was found to be strongly different than in KI crystals not containing Cl-ions. The new relaxation peak attributed to the presence of the Cl- in the close neighborhood of the divalent ion has a relax¬ation time 103 greater than the normal one. A model for the trapping of the divalent ions by the Cl- is proposed. The influence of atomic radius of the divalent and the impurity anion is discussed.

Este trabalho trata de estudos realizados sobre o comportamento das fronteiras dos domínios magnéticos em mono-cristais de (Mn - Zn) Fe2 03 como também das propriedades elásticas de defeitos puntuais em mono-cristais de NaCl: NaF: M++ . Foram aplicadas técnicas do oscilador composto de Marx com controlador automático de velocidade e atenuação ultrassônica, a técnica do pulso-eco ultrassônico e corrente termo-estimulada (I.T.C.) com pressão uniaxial. Para os cristais de NaCl: NaF: M++ , determinamos a simetria e os parâmetros de relaxação que provocam os picos de ITC chamados de B e C. Foi mostrado que o pico C é devido a relaxação de uma vacância entre as posições nn em torno do eixo que passa pelos íons F- M++ , enquanto o pico B é uma relaxação envolvendo uma transição da vacância entre as posições nn e nnn. Para as ferrites as fronteiras dos domínios magnéticos comportam-se elasticamente como dislocações, mostrando uma atenuação ultrassônica que á dependente da amplitude do campo elástico / This work is concerned with the behavior of magnetic domain walls of (Mn - Zn) Fe2O3 single crystals, as well as, with elastic properties of point defects in NaCl: NaF: M++ single crystals. The measurements were carried out using the following experimental techniques: pulse-echo, ITC under uniaxial stress and composite oscillator of the Marx type with automatic control of velocity. For the NaCl: NaF: M ++ crystals the symmetry of the defect that gives rise to ITC peaks B and C was determined, as well as its relaxation parameters. It was shown that peak C is due to vacancy relaxation between nn positions around the axis M++F- ions while peak B is a relaxation involving between the nn and nnn vacancy positions. For the ferrites the magnetic domain walls behave elastically as dislocations therefore having an ultrassonic attenuation that is amplitude dependent on the elastic field

Les transistors organiques sont la base de nombreuses applications de l'électronique organique mais leur rendement électrique ainsi que leur stabilité dans le temps sont encore des verrous technologiques devant être levés. De plus, le phénomène de transport de charges dans ces dispositifs reste une notion encore à l'étude même si différents modèles sont utilisés afin d'expliquer l'effet de champ des transistors organiques. C'est dans ce cadre que s'inscrit cette étude portant sur la caractérisation par spectroscopie d'admittance de jonctions Métal/oxyde/semi conducteur organique/métal. Elle a pour but d'analyser le comportement électrostatique du semi conducteur organique. Les mesures de spectroscopie d'admittance ont été réalisées sur une large bande de fréquence (0.1Hz à 1Mhz) dans laquelle les pertes diélectriques mesurées peuvent être associées à des phénomènes d'orientation (oscillation) de dipôles présents dans la structure. Les réponses en fréquences montrent trois types de comportements dynamiques. A basses fréquences, nous avons observé une diffusion ionique, liée au déplacement d'ions H+ à travers la structure. A hautes fréquences, la réponse est due aux imperfections de l'oxyde. Enfin, aux fréquences intermédiaires, la réponse du semi-conducteur organique est identifiée et attribuée à des dipôles permanents. A partir de ces différentes réponses, un modèle analytique est établi et permet de décrire l'ensemble des réponses dynamiques. Le comportement du semi-conducteur est décrit par la somme d'une fonction de type Debye et de type Cole-Cole. L'analyse des paramètres de ce modèle a permis de mettre en évidence l'influence des dipôles permanents sur la permittivité du film de semi-conducteur organique. Enfin, ce modèle a été validé sur différents échantillons à base de pentacène et a été ensuite appliqué au Poly-3-hexylthiophène. / Organic transistors are vital in many applications of organic electronics but the electrical performance and time stability are technological limitation in order to make this technology reliable. Moreover, in these devices, the charge transport phenomenon has not to be clearly understood even if different models are commonly used to explain the field effect in organic transistors. In this context, this thesis talks about the admittance spectroscopy characterization of metal / oxide / organic semiconductor / metal junctions and analysis the organic semiconductor electrostatic behavior.The admittance spectroscopy measurements were performed on a wide frequency range (0.1Hz to 1MHz) in which the measured dielectric loss may be associated with the orientation phenomenon (as oscillation) of dipoles present in the structure.The frequency responses show three dynamic behaviors. At low frequencies (<10Hz), we observed an ionic diffusion, which is related to the ions movement of H+ through the structure. At high frequencies, (>10kHz) the response is due to defects into the oxide. Finally, at intermediate frequencies, the organic semiconductor response is identified and assigned to the permanent dipoles into the bulk. From these responses, an analytical model is developed and used to describe the dynamic responses. The semi-conductor behavior is described by the sum of a Debye and Cole-Cole function type. The analysis of the model parameters has highlighted the influence of permanent dipoles on the organic semiconductor permittivity. Finally, this model has been agreed on different samples based on pentacene and was applied to the Poly-3-hexylthiophene.

This work consider with monitoring components of komplex permittivity at frequency section of electro-insulation material in process of wetting by dielectric relaxation spectroscopy.

This work deals with measurement capacity and dissipation factor of capacitor with real dielectric in frequency range 20 Hz to 30 MHz. Liquid and solid dielectrics are measured by LCR instruments and by test fixtures, both from company Agilent. Relative permittivity and loss number are calculated for different instruments settings. The general aim is to specify the influence of parameters as frequency, voltage, integration time and thickness of material on the uncertainties of primary and secondary quantities for measurement.

This projects deal with dielectric materials. Characterize definition of dielectric and polarization of dielectric. Shows dielectric relaxation. Specified conception dielectric absorption and interpreted them with DC voltage charging condensator. However, this thesis be engaged in simulation of this process. Output is simulation program of dielectric absorption characteristics for two relaxation mechanism.