Nitrogen- and sulfur-containing conjugated polymers as the hole-transporting materials

A series of novel nitrogen- and sulfur-containing conjugated polymers have been synthesized via an acid-induced self polycondensation of functional monomers with methyl sulfinyl group. They exhibit good solubility in common solvents, such as CHCl3, THF, DMF, DMSO, et al; and thus show excellent film-forming properties. They are used as hole-transport layer (HTL) in two-layer light-emitting diodes (ITO/polymer/Alq3/Mg:Ag). The typical turn-on voltage of these diodes is about 4 similar to 5V. The maximum brightness is about 3440cd/m(2) at 20 V. The maximum efficiency is estimated to be 0.15 Im/W at 10V.

Electrochemiluminescence and its application

The recent development of electrochemiluminescence and its application including quantitative analysis, surface analysis, dynamics research, electron transfer research, and light emitting device are reviewed.

Stimulated emission in blue wavelength region from a copolymer

A dye laser based on the soluble conjugated polymer, Poly[1,8-octanedioxy-2,6-dimethoxy-1,4-phenylene-1,2-ethenylene-1, 4-phenylene-1,2-ethenylene-3,5-dimethoxy-1,4-phenylene], has been fabricated. The laser was pumped by light pulses from the third harmonic radiation of an Nd:YAG laser. The lasing was observed in the blue wavelength region with the peak at 450 nm. The threshold energy is about 19 mu J. The energy conversion yield of the laser is about 3.4%. The maximum peak power of the laser output pulse arrives at about 20 kW.

Efficient green electroluminescent cells using a poly(p-phenylene vinylene) multiblock copolymer sandwiched between carrier-transporting layers

With a newly synthesized poly(p-phenylene vinylene) (PPV) multiblock copolymer used in a triple-layer structure, efficient green light-emitting diodes with low driving voltage have been fabricated. The devices are turned on at 2.5 V, the brightness at 5 V is above 100 cd/m(2) and at 7 V is about 1650 cd/m(2), with an external quantum efficiency of about 1%. (C) 1998 Elsevier Science S.A. All rights reserved.

Effect of polymer chain structure and chain distance on luminescent efficiency

Three kinds of PPV-based copolymers were synthesized and characterized. Their luminescent properties were investigated and discussed by PL spectrum, and time-dependence luminescent spectrum in film and solution stare. The results show that in the range of our study, the PL intensity and lifetime of luminescent decay increase with the increasing length of flexible segments and the solution diluting, indicating the tendency of the increase of luminescent efficiency.

Photoluminesence and electroluminescence of the blue emission of devices based on poly(p-phenylenevinylene) copolymers

Bright blue polymer light-emitting diodes have been fabricated by using the poly(p-phenylenevinylene)-based copolymers with 10 C long aliphatic chains as the electroluminescent layers, PBD in PMMA and Alq(3) as the electron-transporting layers, and aluminum as the cathode. The multilayer structure devices show 190 cd/m(2) light-emitting brightness at 460 nm, 15 V turn-on vol- tage. It is found that the intensities of photoluminescence and electroluminescence (EL) increase with increasing aliphatic chain length, the EL intensity and operation stability of these polymer light-emitting diodes can be improved by reasonable design of the structure.

Synchrotron-laser pump-probe luminescence spectroscopy: Correlation of electronic defect states with x-ray absorption in wide-gap solids

Poolton, Nigel; Hamilton, B.; Evans, D.A., (2005) 'Synchrotron-laser pump-probe luminescence spectroscopy: Correlation of electronic defect states with x-ray absorption in wide-gap solids', Journal of Physics D: Applied Physics 38 pp.1478-1484 RAE2008

Thermal, mechanical and optical modelling of VCSEL packaging

Hybrid OECB (Opto-Electrical Circuit Boards) are expected to make a significant impact in the telecomm switches arena within the next five years, creating optical backplanes with high speed point-to-point optical interconnects. OECB's incorporate short range optical interconnects, and are based on VCSEL (Vertical Cavity Surface Emitting Diode) and PD (Photo Diode) pairs, connected to each other via embedded waveguides in the OECB. The VCSEL device is flip-chip assembled onto an organic substrate with embedded optical waveguides. The performance of the VCSEL device is governed by the thermal, mechanical and optical characteristics of this assembly. During operation, the VCSEL device will heat up and the thermal change together with the CTE mismatch in the materials, will result in potential misalignment between the VCSEL apertures and the waveguide openings in the substrate. Any degree of misalignment will affect the optical performance of the package. This paper will present results from a highly coupled modelling analysis involving thermal, mechanical and optical models. The paper will also present results from an optimisation analysis based on Design of Experiments (DOE).

Field configured assembly: Programmed manipulation and self-assembly at the mesoscale

Field configured assembly is a programmable force field method that permits rapid, "hands-free" manipulation, assembly, and integration of mesoscale objects and devices. In this method, electric fields, configured by specific addressing of receptor and counter electrode sites pre-patterned at a silicon chip substrate, drive the field assisted transport, positioning, and localization of mesoscale devices at selected receptor locations. Using this approach, we demonstrate field configured deterministic and stochastic self-assembly of model mesoscale devices, i.e., 50 mum diameter, 670 nm emitting GaAs-based light emitting diodes, at targeted receptor sites on a silicon chip. The versatility of the field configured assembly method suggests that it is applicable to self-assembly of a wide variety of functionally integrated nanoscale and mesoscale systems.

Hybrid FIB milling strategy for the fabrication of plasmonic nanostructures on semiconductor substrates

The optical properties of plasmonic semiconductor devices fabricated by focused ion beam (FIB) milling deteriorate because of the amorphisation of the semiconductor substrate. This study explores the effects of combining traditional 30 kV FIB milling with 5 kV FIB patterning to minimise the semiconductor damage and at the same time maintain high spatial resolution. The use of reduced acceleration voltages is shown to reduce the damage from higher energy ions on the example of fabrication of plasmonic crystals on semiconductor substrates leading to 7-fold increase in transmission. This effect is important for focused-ion beam fabrication of plasmonic structures integrated with photodetectors, light-emitting diodes and semiconductor lasers.

Orientation effects in copper phthalocyanine films studied by EPR

Organic semiconductors have already found commercial applications in for example displays with organic light-emitting diodes (OLEDs) and great advances are also being made in other areas, such as organic field-effect transistors and organic solar cells. [1] The organic semicondutor group of materials known as metal phthalocyanines (MPc’s) is interesting for applications such as large area solar cells due to their optoelectronic properties coupled with the possibility of easily and cheaply fabricating thin films of MPc’s. [1, 2]

Many of the properties of organic semiconductors, such as magnetism, light absorption and charge transport, show orientational anisotropy. [2, 3] To maximise the efficiency of a device based on these materials it is therefore important to study the molecular orientation in films and to assess the influence of different growth conditions and substrate treatments. X-ray diffraction is a well established and powerful technique for studying texture (and hence molecular orientation)_in crystalline materials, but cannot provide any information about amorphous or nanocrystalline films. In this paper we present a continuous wave X-band EPR study using the anisotropy of the CuPc EPR spectrum [4] to determine the orientation effects in different types of CuPc films. From these measurements we also gain insight into the molecular arrangement of films of CuPc mixed with the isomorphous H2Pc and with C60 in films typical of real solar cell systems.

Caracterização e modificação de heteroestruturas de nitretos do grupo III

Os nitretos binários semicondutores do grupo III, e respetivos compostos, são vastamente estudados devido à sua possível aplicabilidade em dispositivos optoeletrónicos, tais como díodos emissores de luz (LEDs) e LASERs, assim como dispositivos para a eletrónica de elevadas temperatura, potência e frequência. Enquanto se concretizou a comercialização na última década de LEDs e LASERs recorrendo ao ternário In1-yGayN, estudos das propriedades fundamentais estruturais e óticas, assim como de técnicas de processamento no desenvolvimento de novas aplicações de outros ternários do grupo III-N encontram-se na sua fase inicial. Esta tese apresenta a investigação experimental de filmes finos epitaxiais de Al1-xInxN crescidos sobre camadas tampão de GaN e de Al1-yGayN e o estudo do recozimento e implantação de super-redes (SL) compostas por pontos quânticos de GaN (QD) envolvidos por camadas de AlN. Apesar do hiato energético do Al1-xInxN poder variar entre os 0,7 eV e os 6,2 eV e, por isso, numa gama, consideravelmente superior à dos ternários Al1-yGayN e InyGa1-yN, o primeiro é o menos estudado devido a dificuldades no crescimento de filmes com elevada qualidade cristalina. É efetuada, nesta tese, uma caracterização estrutural e composicional de filmes finos de Al1-xInxN crescidos sobre camadas tampão de GaN e de Al1-yGayN usando técnicas de raios-X, feixe de iões e de microscopia. Mostra-se que o Al1-xInxN pode ser crescido com elevada qualidade cristalina quando a epitaxia do crescimento se aproxima da condição de rede combinada do Al1-xInxN e da camada tampão (GaN ou Al1-yGayN), isto é, com conteúdo de InN de ~18%, quando crescido sobre uma camada de GaN. Quando o conteúdo de InN é inferior/superior à condição de rede combinada, fenómenos de relaxação de tensão e deterioração do cristal tais como o aumento da rugosidade de superfície prejudicam a qualidade cristalina do filme de Al1-xInxN. Observou-se que a qualidade dos filmes de Al1-xInxN depende fortemente da qualidade cristalina da camada tampão e, em particular, da sua morfologia e densidade de deslocações. Verificou-se que, dentro da exatidão experimental, os parâmetros de rede do ternário seguem a lei empírica de Vegard, ou seja, variam linearmente com o conteúdo de InN. Contudo, em algumas amostras, a composição determinada via espetrometria de retrodispersão de Rutherford e difração e raios-X mostra valores discrepantes. Esta discrepância pode ser atribuída a defeitos ou impurezas capazes de alterar os parâmetros de rede do ternário. No que diz respeito às SL dos QD e camadas de AlN, estudos de recozimento mostraram elevada estabilidade térmica dos QD de GaN quando estes se encontram inseridos numa matriz de AlN. Por implantação iónica, incorporou-se európio nestas estruturas e, promoveu-se a ativação ótica dos iões de Eu3+ através de tratamentos térmicos. Foram investigados os efeitos da intermistura e da relaxação da tensão ocorridos durante o recozimento e implantação nas propriedades estruturais e óticas. Verificou-se que para fluências elevadas os defeitos gerados por implantação são de difícil remoção. Contudo, a implantação com baixa fluência de Eu, seguida de tratamento térmico, promove uma elevada eficiência e estabilidade térmica da emissão vermelha do ião lantanídeo incorporado nos QD de GaN. Estes resultados são, particularmente relevantes, pois, na região espetral indicada, a eficiência quântica dos LEDs convencionais de InGaN é baixa.

Electrical characterization of metal-oxide-polymer devices for non-volatile memory applications

The objective of this thesis is to study the properties of resistive switching effect based on bistable resistive memory which is fabricated in the form of Al2O3/polymer diodes and to contribute to the elucidation of resistive switching mechanisms. Resistive memories were characterized using a variety of electrical techniques, including current-voltage measurements, small-signal impedance, and electrical noise based techniques. All the measurements were carried out over a large temperature range. Fast voltage ramps were used to elucidate the dynamic response of the memory to rapid varying electric fields. The temperature dependence of the current provided insight into the role of trapped charges in resistive switching. The analysis of fast current fluctuations using electric noise techniques contributed to the elucidation of the kinetics involved in filament formation/rupture, the filament size and correspondent current capabilities. The results reported in this thesis provide insight into a number of issues namely: (i) The fundamental limitations on the speed of operation of a bi-layer resistive memory are the time and voltage dependences of the switch-on mechanism. (ii) The results explain the wide spread in switching times reported in the literature and the apparently anomalous behaviour of the high conductance state namely the disappearance of the negative differential resistance region at high voltage scan rates which is commonly attributed to a “dead time” phenomenon which had remained elusive since it was first reported in the ‘60s. (iii) Assuming that the current is filamentary, Comsol simulations were performed and used to explain the observed dynamic properties of the current-voltage characteristics. Furthermore, the simulations suggest that filaments can interact with each other. (iv) The current-voltage characteristics have been studied as a function of temperature. The findings indicate that creation and annihilation of filaments is controlled by filling and neutralizing traps localized at the oxide/polymer interface. (v) Resistive switching was also studied in small-molecule OLEDs. It was shown that the degradation that leads to a loss of light output during operation is caused by the presence of a resistive switching layer. A diagnostic tool that predicts premature failure of OLEDs was devised and proposed. Resistive switching is a property of oxides. These layers can grow in a number of devices including, organic light emitting diodes (OLEDs), spin-valve transistors and photovoltaic devices fabricated in different types of material. Under strong electric fields the oxides can undergo dielectric breakdown and become resistive switching layers. Resistive switching strongly modifies the charge injection causing a number of deleterious effects and eventually device failure. In this respect the findings in this thesis are relevant to understand reliability issues in devices across a very broad field.

Synthèse de nouveaux matériaux conducteurs comportant des unités aromatiques conjuguées et analyse de leurs propriétés physico-chimiques

Les matériaux conjugués ont fait l’objet de beaucoup de recherches durant les dernières années. Les nouveaux matériaux présentent des propriétés intéressantes que ce soit au niveau optique, électrique, mécanique ou même les trois en même temps. La synthèse reste la difficulté principale dans la fabrication de dispositifs électroniques. Les méthodes utilisées pour y parvenir sont l’électropolymérisation, le couplage de Suzuki ou de Wittig. Ces techniques comportent encore de nombreuses contraintes et s’avèrent difficilement réalisables à grande échelle. Les thiophènes, les pyrroles et les furanes ont démontré une bonne conductibilité et une bande de conduction basse due à une conjugaison accrue. L’objectif ici est de synthétiser des oligomères principalement composés de thiophènes dans le but d’en caractériser les propriétés spectroscopiques, électrochimiques et de conduction. La synthèse est souvent l’étape délicate de la fabrication de matériaux conjugués. Nous présentons ici une méthode de synthèse simple par modules avec des unités hétérocycliques. Les modules complémentaires sont attachés par condensation entre un aldéhyde et une amine menant à la formation d’un lien robuste, l’azomethine. Les résultats des propriétés photophysiques et électrochimiques de ces matériaux conjugués seront présentés. En ayant recours à différents groupes électrodonneurs et électroaccepteurs, en variant le degré de conjugaison ou en utilisant différents hétérocycles, les propriétés spectroscopiques, électrochimiques et de bande de conduction peuvent être adaptées à volonté, ce qui en fait des matériaux aux propriétés modelables. Ces nouvelles molécules seront analysées pour en déceler les propriétés recherchées dans la fabrication d’OLED. Nous explorerons les domaines de l’oxidation electrochimique réversible et de la polymérisation menant à la fabrication de quelques prototypes simples.

Développement de composés conjugués en étoile de première génération incluant des liens azométhines et études électrochimiques et photophysiques

Les matériaux conjugués sont de nos jours très utilisés dans de nombreuses applications ainsi qu’en recherche. L’enchainement des liaisons π-σ-π permet la délocalisation des électrons et d’obtenir différentes propriétés comme la conduction, la fluorescence, la chélation, etc. Ainsi, de nombreux dispositifs utilisent ces caractéristiques en vue d’obtenir de nouveaux matériaux révolutionnaires comme les cellules solaires, les transistors à effet de champs, les dispositifs électrochromiques, etc.. Les dispositifs électrochromiques font partie des dispositifs en vogue. Ils sont capables de changer de couleur selon le potentiel électrique appliqué. Ils se distinguent par la simplicité du mode de conception et ils ne nécessitent pas de fonctionner dans des conditions drastiques comme une atmosphère contrôlée. Ces dispositifs sont actuellement utilisés et commercialisés comme fenêtre intelligente, camouflage, papier électronique et carte de visite personnalisée pour n’en nommer que quelques-uns. Deux propriétés sont essentielles pour que des composés puissent être utilisés dans ces familles de dispositifs : la réversibilité à l’oxydation et la stabilité à l’air et à la lumière. Dans le groupe de recherche du professeur W.G. Skene, l’axe principal de recherche est basé sur la conception de nouveaux matériaux conducteurs comportant des liaisons azométhines. Les principaux matériaux étudiés sont des dérivés de thiophènes et de fluorènes. De précédents résultats ont montré que plusieurs produits issus de la réaction de condensation entre les dérivés du 2,5-diaminothiophène et de thiophènes diformylés menaient à des produits possédant d’excellentes propriétés photophysiques et électrochimiques. C’est en partant de ces résultats encourageants qu’il a été choisi de synthétiser une nouvelle famille de produits avec un nouveau substrat fonctionnalisé. Ce dernier possède d’excellentes propriétés électrochimiques et photophysiques : la triphénylamine. Deux familles de produits ont été synthétisées qui possèdent toutes comme cœur une triphénylamine. Cette dernière a été modifiée de façon à créer une, deux ou trois liaisons azométhines avec différents thiophènes. Deux dérivés du thiophène ont été choisis afin d’étudier l’influence des groupements donneurs et accepteurs sur ces nouveaux types de composés encore jamais étudiés. Les résultats des différentes synthèses et analyses ont été effectués par RMN, spectrométrie de masse, spectrométrie d’absorbance UV-Visible, fluorescence et voltampérométrie cyclique sont rapportées dans le présent recueil.