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Polymer light emitting electrochemical cells (LECs) are solid-state devices containing an active layer blend of luminescent polymer, ion transport material and salt sandwiched between two electrodes. They operate on the principal of in situ electrochemical doping. Doping entails the injection of electronic charge from the electrodes, causing the reduction/oxidization of the luminescent polymer, and accompanied by charge compensation through the redistribution of salt counter-ions. Due to the high conductivity of the doped polymer, a fully turned on LEC has a dramatically reduced contact and bulk resistance. This gives the LEC certain intrinsic advantages such as balanced charge injection, low operating voltage and high quantum efficiencies, even when stable metal or symmetric electrodes are used. These properties have led to the popular assumption that the electrode work function is not a critical device parameter for LEC operation. In this thesis, I describe my original research to determine how the electrode composition influences LEC performance. A series of sandwich and planar configuration LECs with various electrodes on identical MEH-PPV (poly[5-(2-ethylhexyloxy)-2-methoxy-1,4-phenylene vinylene]):PEO (poly ethylene oxide):LiTr (Lithium trifluoromethanesulfonate) based films are constructed. I demonstrate that the doping profile, doping propagation speed, emission zone shape, emission zone location, electro-luminescence (EL) turn-on, and EL efficiency are all strongly affected by the choice of electrode materials. LECs with asymmetrical electrodes optimized for both electron and hole injection result in the best overall performance. Using an optimized electrode configuration, I am able to realize extremely large crown ether based planar LECs. MEH-PPV: dicyclohexano-18-crown-6 (DCH18Cr6): LiTr and 108GE:DCH18Cr6:LiTr devices with various symmetric and asymmetric electrode configurations were constructed, where 108GE is the fluorene copolymer poly[(9,9-dioctyl-2,7-divinylene-fluorenylene)-alt-co-(2-methoxy-5-(ethylhexyloxy)-1,4-phenylene)]. I demonstrate ii i and image the first ever crown ether-based planar LECs with millimeter inter-electrode spacing. Due to minimal phase separation, crown ether-based LECs display highly uniform doping propagation and very smooth emission zones. Junction relaxation, de-doping and reverse bias operation experiments are also presented, and results compared to behavior in PEO based LECs. Additionally, I demonstrate that crown ether-based LECs do not exhibit frozen junction behavior at room temperature. / Thesis (Master, Physics, Engineering Physics and Astronomy) -- Queen's University, 2008-09-23 16:15:06.569

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No description available.

Developing organic light-emitting diodes (OLEDs) as the next generation display devices is not only of industrial interest, but also a scientific challenge in and of itself that requires multi-disciplinary efforts to make the technology successful. Thermally activated delayed fluorescence (TADF) is a recent breakthrough in OLED technology whose prime value is to enable purely organic emitters to recruit the dark triplet excitons in the device, thus avoiding expensive and toxic rare metal based emitters. This thesis is centred on TADF and contains work in three major areas. Firstly, novel ionic TADF emitters were designed for use in light-emitting electrochemical cells (LEECs), which is an alternative electroluminescent device technology to OLEDs, with a much simplified fabrication procedure and architecture. The vast majority of these ionic emitters are based on reported TADF scaffolds where the donors were tethered with an imidazolium hexafluorophosphate group to obtain the ionic character required for LEEC devices (TL and BTL series, Chapter 2). On the other hand, TADF emitters with a carboxylate group were also designed which act as both acceptor and intrinsic charged functionality for LEEC applications (CTL series, Chapter 2). Secondly, attempts were made to create novel TADF molecular scaffolds in order to enrich the current library of TADF emitters. Research efforts were focused on polyaromatic moieties such as anthracene (An series, Chapter 4) and fluoranthene (FA series, Chapter 4) that are seldom reported in TADF literature. In addition, TADF emitters with phosphine oxide as the acceptor group have also been studied (PO series, Chapter 5). Lastly, structure-property relationship studies of TADF emitters were undertaken as a function of tuning of donor and acceptor functionalities using both theoretical and experimental approaches in order to gain more insight for designing desirable TADF emitters (Chapter 3).

Made available in DSpace on 2014-10-09T12:34:05Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:48Z (GMT). No. of bitstreams: 0 / Eletrodos à base de carbono, como os eletrodos de troca iônica, entre outros, têm aplicação principalmente no tratamento de efluentes industriais e rejeitos radioativos. Carbono é também amplamente utilizado em células a combustível como substrato para os eletrocatalisadores, por possuir elevada área superficial, que supera a sua área geométrica. O conhecimento desta superfície ativa total é importante na determinação das condições de operação de uma célula eletroquímica no que diz respeito às correntes a serem aplicadas (densidade de corrente). No presente estudo foram utilizadas duas técnicas eletroquímicas na determinação da área superficial ativa de eletrodos de carbono vítreo e poroso e eletrodos de troca iônica: espectroscopia de impedância eletroquímica (EIE) e voltametria cíclica (VC). Os experimentos foram realizados com soluções de KNO3 0,1 mol.L-1 em célula eletroquímica de três eletrodos: eletrodo de trabalho à base de carbono, eletrodo auxiliar de platina e eletrodo de referência de Ag/AgCl. Os eletrodos de carbono vítreo e de carbono poroso utilizado possuíam uma área geométrica de 3,14 x 10-2 cm2 e 2,83 10-1 cm2, respectivamente. O eletrodo de troca iônica foi preparado misturando-se grafite, carbono, resina de troca iônica e um aglutinante, sendo esta mistura aplicada em três camadas sobre feltro de carbono, utilizando-se nos experimentos uma área geométrica de 1,0 cm2. Por EIE determinou-se diretamente a capacitância dos materiais dos eletrodos (Cd) utilizando-se os diagramas de Bode. O valor de 172 μF.cm-2 encontrado para o carbono vítreo está de acordo com a literatura (~200 μF.cm-2). Por VC, variando a velocidade de varredura de 0,2 a 2,0 mV.s-1, determinou-se a capacitância CdS (S=área superficial ativa) na região da dupla camada elétrica (DCE) para cada um dos materiais, Por EIE, foram determinados os valores de Cd de 3,0 x 10-5 μF.cm-2 e de 11,0 x 103 μF.cm-2 para os eletrodos de carbono poroso e de troca iônica, respectivamente, o que possibilitou a determinação das áreas superficiais ativas de 3,73 x 106 cm2 e 4,72 cm2. Portanto, o uso combinado das técnicas de EIE e VC mostra-se promissor para o cálculo das áreas superficiais ativas de eletrodos à base de carbono. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

A polymer light-emitting electrochemical cell (LEC) is a solid-state polymer device operating according to in situ electrochemical doping and the formation of a light-emitting polymer p-n junction. This operating mechanism, however, has been the subject of much debate. Planar LECs with millimeter scale interelectrode spacings offer great advantages for directly observing the electrochemical doping process. Photoluminescence quenching and the formation of a light-emitting junction have been observed in planar polymer LECs, demonstrating the existence of electrochemical doping. The chemical potential difference between the p- and n-doped regions creates a built-in potential/electric field in the junction region, which can be probed by measuring the optical beam induced current (OBIC). This study utilizes a versatile and easy-to-use method of performing OBIC analysis. The OBIC and photoluminescence profiles of LECs have been simultaneously measured by scanning a focused light beam across large planar LECs that have been turned on and cooled to freeze the doping profile. The photoluminescence intensity undergoes a sharp transition between the p- and n-doped regions. The OBIC photocurrent is only observed in the transition region that is narrower than the width of the excitation beam, which is about 35 μm. The results depict a static planar polymer p-n junction with a built-in electric field pointing from n to p. The electrode interfaces do not produce a measurable photocurrent indicating ohmic contact. / Thesis (Master, Physics, Engineering Physics and Astronomy) -- Queen's University, 2013-05-28 12:52:14.171

As células eletroquímicas emissoras de luz são dispositivos eletroluminescentes cuja camada ativa é uma mistura de um material eletroluminescente e um eletrólito sólido a base de sais de metais alcalinos, geralmente lítio. A presença dos íons na camada ativa modificam o mecanismo de funcionamento das células quando comparadas ao diodos emissores de luz. Nas células, a concentração de íons nas interfaces eletródicas forma uma dupla camada elétrica que auxilia a injeção de cargas na camada ativa, por sua vez e na presença dos íons, o material eletroluminescente sofre dopagem se tornando condutor, os portadores injetados irão se encontrar numa região da camada ativa recombinando-se e emitindo luz. Compreender as interações dos diversos materiais que formam a camada ativa é fundamental para otimizar o desempenho do dispositivo. Neste trabalho estudamos a interação do ADS108GE, um polímero luminescente, e um eletrólito sólido a base de poli (óxido de etileno) (PEO) e LiCF3SO3 ou LiB(C2O4)2. O LiB(C2O4)2 foi sintetizado neste trabalho para estudar a viabilidade de se substituir o LiCF3SO3 que é o sal tipicamente utilizado nas células. Foram utilizadas técnicas de Análise Dinâmico-Mecânica (DMA), Espectroscopia Vibracional no Infravermelho (FTIR), Microscopia de Força Atômica (AFM), Difração de Raios-X (DRX), Microscopia Óptica de Varredura no Campo Próximo (IR-SNOM), Impedância Elétrica e Voltametria Cíclica. Os resultados de DMA em conjunto com DRX e AFM, permitiram estabelecer que o aumento da concentração de sal contribui para mudanças morfológicas que se relacionam com o aumento da fração de fase amorfa e independem do ânion, demonstrando que estes efeitos estão ligados à interação PEO-Lítio. Por outro lado, os espectros de FTIR e resultados de impedância elétrica mostram que o aumento da concentração de LiCF3SO3 gera agregação do sal diminuindo a condutividade, a mobilidade iônica e o número de portadores efetivos, enquanto para o LiB(C2O4)2 não se observa tal efeito. O IR-SNOM permitiu identificar nas misturas utilizadas como camada ativa que o ADS108GE forma estruturas globulares embebidas numa matriz de PEO. Do ponto de vista operacional, as células a base de LiB(C2O4)2 possuem uma eficiência maior do que as a base LiCF3SO3 e maior estabilidade. / Light-emitting electrochemical cells are electroluminescent devices whose active layer is a mixture of an electroluminescent material and a solid electrolyte based on alkaline salts, usually a lithium salt. The ions within thea ctive layer change the devices working mechanism when compared to light emitting diodes. In the cells, there is an ion build up at electrodic interfaces creating an electric double layer allowing charge injection in the active layer. The electroluminescent material is doped by these injected charges becoming conductive. These injected charges recombine emitting light. In order to optimize devices performance, it is fundamental to study materials interactions when mixed as an active layer. In this work, we studied the interactions between ADS108GE, a luminescent polymer, and a solid electrolyte based on polyethylene oxide and LiCF3SO3 or LiB(C2O4)2. LiB(C2O4)2 was prepared in this work to assess its feasibility as LiCF3SO3 substitution which is the typical choice. We used the following techniques in this work: Dynamical Mechanical Analysis (DMA), Infrared Vibration Spectroscopy (FTIR), Atomic Force Microscopy AFM), X-Ray Diffraction (XRD), Infrared Scanning Near-Field Optical Microscopy (IRSNOM), Electrical Impedance and Cyclic Voltammetry. From DMA, XRD and AFM results, it is possible to conclude that as we increase salt concentration, the active layer has morphological changes related to an increasing fraction of an amorphous phase. These effects are anion independent showing that PEO-Li interactions are the responsible ones. On the other hand, FITR and electrical impedance experiments show that increasing LiCF3SO3 concentration leads to salt aggregation decreasing conductivity, ionic mobility and the effective number of carriers, moreover, we do not see this effect with LiB(C2O4)2. IR-SNOM identified that ADS108GE were organized as globular structures embedded in a PEO matrix. The cells made with LiB(C2O4)2 were more efficient than those based on LiCF3SO3 and were even more stable.

abstract: Microbial electrochemical cells (MxCs) are a novel technology that use anode-respiring bacteria (ARB) to bioremediate wastewaters and respire an electrical current, which can then be used directly to produce value-added products like hydrogen peroxide (H2O2). Ninety-five percent of the world’s H2O2 is currently produced using the anthraquinone process, whose production requires expensive and potentially carcinogenic catalysts and high amounts of electricity. However, the amount of H2O2 that can be produced from these microbial peroxide-producing cells (MPPCs) has not been thoroughly investigated. Predicting potential H2O2 production in MxCs is further complicated by a lack of mathematical models to predict performance utilizing complex waste streams like primary sludge (PS). A reactor design methodology was developed for MPPCs to systematically optimize H2O2 production with minimal energy consumption. H2O2 stability was evaluated with different catholytes, membranes, and catalysts materials, and the findings used to design and operate long-term a dual-chamber, flat-plate MPPC using different catholytes, ferrochelating stabilizers, and hydraulic retention times (HRT). Up to 3.1 ± 0.37 g H2O2 L-1 was produced at a 4-h HRT in an MPPC with as little as 1.13 W-h g-1 H2O2 power input using NaCl catholytes. Attempts to improve H2O2 production by using weak acid buffers as catholytes or ferrochelating stabilizers failed for different reasons. A non-steady-state mathematical model, MYAnode, was developed combinging existing wastewater treatment, anode biofilm, and chemical speciation models to predict MxC performance utilizing complex substrates. The model simulated the large-scale trends observed when operating an MPPC with PS substrate. At HRTs ≥ 12-d, the model demonstrated up to 20% Coulombic recovery. At these conditions, ARB required additional alkalinity production by ≥ 100 mgVSS/L of acetoclastic methanogens to prevent pH inhibition when little influent alkalinity is available. At lower HRTs, methanogens are unable to produce the alkalinity required to prevent ARB inhibition due to washout and rapid acidification of the system during fermentation. At ≥ 100 mgVSS/L of methanogens, increasing the diffusion layer thickness from 500 to 1000 μm improved Coulombic efficiency by 13.9%, while increasing particulate COD hydrolysis rates to 0.25/d only improved Coulombic efficiency by 3.9%. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2018

This thesis presents a comparative study between two silver nanoparticle inks that were deposited using a Drop-on-Demand (DoD) inkjet printer, aiming at finding a functional ink that can be used to print electrodes in Light-emitting Electrochemical Cells (LECs). To achieve this, a DoD inkjet printer was installed and an acquaintance with the printer was attained. Among the two inks, one was employed as received while the other was reformulated, and successful deposition of both the inks was observed. During the reformulation process, it was seen that the highly volatile tetrahydrofuran (THF) solvent can be used to improve the ink properties, in contrast to what is recommended. After that, the inks were deposited on UV-ozone treated glass substrates, sintered at an elevated temperature under ambient conditions, and their specific resistances and thicknesses were measured. Finally, the inks were used to print the anode in a structured sandwich-cell LEC. The performance comparison was conducted by observing the emitted light of the LECs. The results indicate that the reformulated ink performs better, probably due to the lower silver concentration that results in flatter surface, which in turn effectively alleviates shorts.