A técnica de injeção de cargas por feixe eletrônico em materiais poliméricos pode ser utilizada como uma importante ferramenta no estudo das propriedades elétricas destes materiais. Fenômenos tais como a emissão eletrônica secundária, o transporte e armazenamento de portadores de carga no volume do material, fenômenos de injeção e condutividade induzida por radiação podem ser observados em películas finas de dielétricos lançando mão desta poderosa técnica. Neste trabalho, utilizamos um canhão de elétrons de energia variável (O a 10 keV) na irradiação de amostras de polianilinas, por nós sintetizadas, para o estudo da emissão secundária e de transporte no volume. Alguns experimentos foram também realizados com o poli(fluoreto de vinilideno), que é um polímero bem mais resistivo que as polianilinas. As medidas de emissão eletrônica foram feitas em circuito aberto, enquanto as medidas de transporte foram obtidas em circuito fechado. Neste segundo tipo de configuração, procuramos fazer uma análise do comportamento da corrente através da amostra pela observação de transientes rápidos (da ordem de 10 ms) de corrente gerados pela injeção de pacotes de carga de penetração bem definida a partir da superfície bombardeada. Propriedades elétricas intrínsecas como a condutividade do material e a permissividade elétrica, e extrínsecas como a condutividade na região irradiada foram utilizadas como parâmetros no ajuste dos resultados experimentais. / Charge injection in polymeric materials by electron beam is a powerful technique in the study of electrical properties of such materials. Secondary emission, transport and storage phenomena, as well as radiation-induced conductivity are among the subjects related to dielectrics that can be investigated. At present work we used an electron beam system (O to 10 keV) to irradiate polyaniline films, synthesized in our laboratory, and to perform studies of secondary emission and transport phenomena. Some experiments were also carried out with poly(viny1idene fluoride), a more resistivity polymer. Secondary emission measurements were carried out in an open-circuit configuration while the transport ones used a short circuit mode. Fast transient phenomena (about 10 ms) were also studied in details. Intrinsic electric properties, such as conductivity and dielectric constant, and extrinsic ones, like the induced conductivity in the irradiated region of the sample, were obtained in the fitting between the model and the experimental results.

In dieser Arbeit werden Speichertransistoren mit Oxid-Nitrid-Oxid-Speicherschicht und lokaler Ladungsspeicherung untersucht, die zur nichtflüchtigen Speicherung von Informationen genutzt werden. Charakteristisch für diese Transistoren ist, dass an beiden Enden des Transistorkanals innerhalb der Isolationsschicht Informationen in Form von Ladungspaketen unabhängig und getrennt voneinander gespeichert werden. Für das Auslesen, Programmieren und Löschen der Speichertransistoren werden die physikalischen Hintergründe diskutiert und grundlegende Algorithmen zur Implementierung dieser Operationen auf einer typischen Speicherfeldarchitektur aufgezeigt. Für Standard-MOS-Transistoren wird ein Kurzkanal-Schwellspannungsmodell abgeleitet und analytisch gelöst. Anhand dieser Modellgleichung werden die bekannten Kurzkanaleffekte betrachtet. Weiterhin wird ein Modell zur Berechnung des Drainstroms von Kurzkanaltransistoren im Subthreshold-Arbeitsbereich abgeleitet und gezeigt, dass sich die Drain-Source-Leckströme bei Kurzkanaltransistoren vergrößern. Die Erweiterung des Schwellspannungsmodells für Standard-MOS-Transistoren auf den Fall der lokalen Ladungsspeicherung innerhalb der Isolationsschicht erlaubt die Ableitung eines Schwellspannungsmodells für Oxid-Nitrid-Oxid-Transistoren mit lokaler Ladungsspeicherung. Dieses Modell gestattet die qualitative und quantitative Diskussion der Erhöhung der Schwellspannung durch die lokale Injektion von Ladungsträgern beim Programmiervorgang. Weiterhin ist es mit diesem Modell möglich, die Trennung der an beiden Kanalenden des Transistors gespeicherten Informationen beim Auslesevorgang qualitativ zu erklären und diese Bittrennung in Abhängigkeit von der Drainspannung zu berechnen. Für Langkanalspeichertransistoren wird eine analytische Näherungslösung des Schwellspannungsmodells angegeben, während das Kurzkanalverhalten durch die numerische Lösung der Modellgleichung bestimmt werden kann. Für Langkanalspeichertransistoren wird ein Subthreshold-Modell zur Berechnung des Drainstroms abgeleitet. Dieses Modell zeigt, dass sich die Leckströme von programmierten Speichertransistoren im Vergleich zu Standard-MOS-Transistoren gleicher Schwellspannung vergrößern. Die Ursache dieses Effekts, die Verringerung der Subthreshold-Steigung von Transistoren im programmierten Zustand, wird analysiert. Für einige praktische Beispiele wird die Anwendung der hergeleiteten Modellgleichungen beim Entwurf von Flash-Speichern demonstriert. / In this work, memory transistors with an oxide-nitride-oxide trapping-layer and local charge storage, which are used for non-volatile information storage, are examined. Characteristic for these transistors is an independent and separated storage of information by charge packages, located at both sides of the transistor channel, in the insulation layer. The physical backgrounds for reading, programming and erasing the memory transistors are discussed, and basic algorithms are shown for implementing these operations on a typical memory array architecture. For standard MOS-transistors a short channel threshold model is derived and solved analytically. By using these model equations, the known short channel effects are considered. Further, a model for calculating the drain current of short channel transistors in the subthreshold operation region is derived. This model is used to show the increase of drain-source leakage currents in short channel transistors. By extending the standard MOS-transistor threshold voltage model for local charge storage in the insulation layers, the derivation of a threshold voltage model for oxide-nitride-oxide transistors with local charge storage is enabled. This model permits the quantitative and qualitative discussion of the increase in threshold voltage caused by local injection of charges during programming. Furthermore, with this model, the separation of the information, which are stored at both sides of the transistor channel, in the read-out operation is explained qualitatively, and the bit separation is calculated dependent on the drain voltage. For long channel memory transistors an analytical approximation of the threshold voltage model is given, whereas the short channel behaviour can be determined by solving the model equation numerically. For long channel memory transistors, a subthreshold model for calculating the drain current is derived. This model shows the increase in leakage current of programmed memory transistors in comparision to standard MOS-transistors. The root cause of this effect, the reduced subthreshold swing of transistors in the programmed state, is analysed. The application of the derived model equations for the development of flash memories is demonstrated with some practical examples.

Améliorer notre compréhension des mécanismes de transport/transfert de charges et de stockage de charges dans les films d'oxyde métallique semi-conducteur mésoporeux transparents (fonctionnalisés ou non par des chromophores redox-actifs) dans des électrolytes aqueux est d'une importance fondamentale pour le développement et l'optimisation d'une large gamme de dispositifs de production ou de stockage d'énergie éco-compatibles et/ou éco-durables (cellules solaires à colorants, batteries, photoélectrolyseurs, ….). Dans ce but, des films de TiO2 semi-conducteur mésoporeux préparés par dépôt sous incidence rasante (GLAD-TiO2) ont été sélectionnés pour leur grande surface spécifique, leur morphologie bien contrôlée, leur transparence élevée dans le visible et leur semiconductivité bien définie qui peut être facilement ajustée par l’application d’un potentiel externe, autorisant ainsi leur caractérisation aisée par spectroélectrochimie en temps réel. Nous avons d'abord étudié le transfert et transport de charges dans des électrodes GLAD-ITO et GLAD-TiO2 fonctionnalisées par une porphyrine de manganèse redox-active jouant à la fois le rôle de chromophore et de catalyseur. Nous avons démontré que la réponse électrochimique des électrodes ainsi modifiées, enregistrée en l'absence ou en présence du substrat O2, dépend fortement de la conductivité du film mésoporeux. En utilisant la voltamétrie cyclique couplée à la spectroscopie d'absorption UV-visible, nous avons pu extraire des informations clés telles que la vitesse du transfert d'électrons hétérogène entre le chromophore redox immobilisé et le matériau semi-conducteur, et aussi pu rationaliser le comportement électrochimique spécifique obtenu sur un film GLAD-TiO2 modifié par la porphyrine en condition catalytique. En parallèle, nous avons développé un procédé de fonctionnalisation de ces films d'oxyde métallique mésoporeux (en l’occurrence des films GLAD-ITO) par électrogreffage de sels d'aryldiazonium générés in situ, permettant d'obtenir des électrodes fonctionnalisées avec un taux de recouvrement surfacique élevé et une stabilité dans le temps particulièrement bonne en conditions hydrolytiques. Nous avons également étudié le stockage de charges au sein d’électrodes GLAD-TiO2 dans divers électrolytes aqueux. Nous avons notamment démontré pour la première fois qu’une insertion rapide, massive et réversible de protons peut être effectuée dans des films de TiO2 nanostructurés amorphes immergés dans un tampon aqueux neutre, le donneur de protons étant alors la forme acide faible du tampon. Nous avons également démontré que ce processus de stockage d’électrons couplé à l’insertion de protons peut se produire sur toute la gamme de pH et pour un vaste panel d'acides faibles organiques ou inorganiques, mais aussi de complexes aqueux d'ions métalliques multivalents, à condition que le potentiel appliqué et le pKa de l'acide faible soient correctement ajustés. / Better understanding of the mechanisms of charge transport/transfer and charge storage in transparent mesoporous semiconductive metal oxide films (either functionalized or not by redox-active chromophores) in aqueous electrolytes is of fundamental importance for the development and optimization of a wide range of safe, eco-compatible and sustainable energy producing or energy storage devices (e.g., dye-sensitized solar cells, batteries, photoelectrocatalytic cells, …). To address this question, mesoporous semiconductive TiO2 films prepared by glancing angle deposition (GLAD-TiO2) were selected for their unique high surface area, well-controlled morphology, high transparency in the visible, and well-defined semiconductivity that can be easily adjusted through an external bias, allowing thus their characterization by real-time spectroelectrochemistry. We first investigated charge transfer/transport at GLAD-ITO and GLAD-TiO2 electrodes functionalized by a redox-active manganese porphyrin that can play both the role of chromophore and catalyst. We demonstrate that the electrochemical response of the modified electrodes, recorded either in the absence or presence of O2 as substrate, is strongly dependent on the mesoporous film conductivity. By using cyclic voltammetry coupled to UV-visible absorption spectroscopy, we were able to recover some key information such as the heterogeneous electron transfer rate between the immobilized redox-active dye and the semiconductive material, and also to rationalize the specific electrochemical behavior obtained at a porphyrin-modified GLAD TiO2 film under catalytic turnover. In parallel, we developed a new functionalization procedure of mesoporous metal oxide films (GLAD-ITO in the present case) by electrografting of in-situ generated aryldiazonium salts, allowing for modified electrodes characterized by both a high surface coverage and a particularly good stability over time under hydrolytic conditions. Also, we investigated charge storage at GLAD-TiO2 electrodes under various aqueous electrolytic conditions. We notably evidenced for the first time that fast, massive, and reversible insertion of protons can occur in amorphous nanostructured TiO2 films immersed in near neutral aqueous buffer, with the proton donor being the weak acid form of the buffer but not water. We also demonstrated that this proton-coupled electron charge storage process can occur over the entire range of pH and for a wide range of organic or inorganic weak acids, but also of multivalent metal ion aquo complexes, as long as the applied potential and pKa of weak acid are properly adjusted.